JP2013541516A - Composition containing pyripyropene insecticide and adjuvant - Google Patents

Abstract

【選択図】なしA pesticidal composition containing a pyripyropene insecticide and an adjuvant. The present invention relates to a composition comprising a pyripyropene pesticide of formula (I) or (II) as defined below and an adjuvant. The invention also relates to methods for preparing and applying such compositions, as well as some uses of such compositions and finally seeds comprising said composition. The invention also relates to an aqueous pesticidal formulation comprising a pesticidal compound of the formula I as defined in claim 1 in the form of microparticles suspended in an aqueous liquid.
[Chemical 1]

[Selection figure] None

Description

  The present invention relates to a composition comprising a pyripyropene pesticide of formula I or II as defined below and an adjuvant. The invention also relates to a pesticidal formulation in the form of a suspension concentrate. The invention also relates to a crystalline hydrate of a pyripyropene pesticide of formula I as defined below.

  Various problems can be faced when preparing pesticide formulations of pesticidal compounds. One problem is that the pesticidal activity of compounds with pesticidal activity may be affected in some way in pesticide formulations. Thus, one of the disadvantages of known pesticide formulations of pesticides is that the pesticide activity, such as insecticidal activity, of the pesticide active ingredient in such pesticide formulations is affected and potentially reduced .

Pyripyropene pesticide of formula (I)

(Hereinafter also referred to as “Insecticide A”) is known from WO2009 / 081851 (Example, Compound 4) and belongs to the class of pyripyropene derivatives.

  WO2009 / 081851 discloses various pesticide formulations of insecticide A and additives useful for the pesticide formulations.

  EP2 119 361 and EP1 889 540 disclose various pesticide formulations of pyripyropene derivatives and additives useful in the pesticide formulations.

  The pyripyropene pesticide of formula (I) can be prepared by the method described in WO2006 / 129714 or EP2 186 815.

For example, pyripyropene A produced by the method described in Journal of Society of Synthetic Organic Chemistry, Japan (1998), Vol. 56, No. 6, pp. 478-488 or WO94 / 09417 (in this specification, the following The formula II pyripyropene pesticides) can be used, for example, as starting materials for the preparation of further pyripyropene derivatives.

  Pyripyropene A (hereinafter also referred to as “insecticide B”) has inhibitory activity against ACAT (acyl-CoA: cholesterol acyltransferase), for example, Japanese Patent No. 2993767 (Japanese Patent Laid-Open No. 1992-360895) and As described in Journal of Antibiotics (1993), 46 (7), pp. 1168-9, it is expected to be applied for the treatment of diseases induced by cholesterol accumulation.

  Furthermore, Applied and Environmental Microbiology (1995), 61 (12), pages 4429-35, Pilipiropene A ("Insecticide B") itself has insecticidal activity against larvae of American tobacco moth (Helicoverpa zea). It is described. Furthermore, WO2004 / 060065 describes that pyripyropene A has an insecticidal activity against larvae (Plutella xylostella L) larvae and Tenebrio molitor L.

  Several problems are encountered when trying to provide an agricultural formulation of a pyripyropene derivative, in particular of the formula I or II. One problem associated with the pyripyropene derivatives of formulas I and II is that the formulation stability of these derivatives in aqueous formulations is low and the dilution stability of the formulation is low, which causes the active ingredient particles to settle, Or there is a risk of aggregation. Another problem that can be faced is that the pesticidal activity of compounds with pesticidal activity can be negatively affected in some way in pesticide formulations. Thus, a further disadvantage of agrochemical formulations and compositions of the pyripyropene derivatives of formula I or II is that the insecticidal activity of the pyripyropene derivatives of formula I or II is affected and potentially reduced.

WO2009 / 081851 EP2 119 361 EP1 889 540 WO2006 / 129714 EP2 186 815 WO94 / 09417 Japanese Patent No. 2993767 (Japanese Patent Laid-Open No. 1992-360895) WO2004 / 060065

Journal of Society of Synthetic Organic Chemistry, Japan (1998), 56, 6, 478-488 Journal of Antibiotics (1993), 46 (7), 1168-9 Applied and Environmental Microbiology (1995), 61 (12), pp. 4429-35

  Accordingly, one object of the present invention is to find a method for stabilizing, improving, increasing and / or prolonging the pesticidal activity of pyripyropene derivatives of formulas I and II in agrochemical formulations. A further object of the present invention is to provide excellent formulation stability of pyripyropene derivatives in aqueous formulations, particularly aqueous suspension concentrates.

  Improvement of the insecticidal activity of a pyripyropene of formula I in an agrochemical formulation is another aspect of the present invention. It is desirable to develop new compositions that control pests, including the piripyropene of formula I itself, that have effective insecticidal activity. Accordingly, one object of the present invention is to find a method for stabilizing, improving, increasing and / or prolonging the insecticidal activity of insecticide A.

  Improvement of the insecticidal activity of insecticide B in an agrochemical formulation is a further aspect of the present invention. It is desirable to develop new compositions that control pests, including insecticide B itself as a naturally occurring insecticide with effective insecticidal activity. Therefore, another object of the present invention was also to find a method for stabilizing, improving, increasing and / or prolonging the insecticidal activity of insecticide B.

  These objects and further objects are solved by an agrochemical composition comprising a pyripyropene pesticide of formula I or II and at least one adjuvant.

  The invention also relates to methods for preparing and applying such compositions, as well as some uses of such compositions. In particular, the present invention also relates to a method for preparing said composition comprising the step of contacting, in particular mixing, a pyripyropene pesticide of formula I or II or an agricultural formulation thereof with an adjuvant.

  The invention also provides a) providing a composition containing a pyripyropene pesticide of formula I or II, b) providing a composition containing an adjuvant, c) steps a) and b And a step of contacting the composition with water to obtain an aqueous tank mix.

  Furthermore, the present invention relates to the use of an adjuvant to increase the efficiency of a pyripyropene pesticide of formula I or II, and a) a pyripyropene of formula I or II, and b) an adjuvant. Relates to a kit of parts which is included as a separate component.

  A further subject matter is a method for protecting a plant from attack or parasitism by insects, ticks or nematodes, wherein the plant or soil or water on which the plant grows is contacted with a pesticidally effective amount of said composition. A method of controlling insects, spiders or nematodes, wherein said insect, mite or nematode, or their food supply, habitat, hotbed or their location and said pesticide effective amount A method comprising contacting the composition; a method for protecting plant propagation material comprising contacting the plant propagation material, preferably seed, with a pesticide effective amount of the composition; and Finally, seeds containing the composition.

  The pyripyropene pesticide compounds of formula I described in the prior art tend to form aggregates or coarse particles that tend to settle out of the formulation, making it difficult to formulate as a stable aqueous formulation It was also found. In addition, when such an aqueous formulation is diluted with water, the pesticidal compound may settle out of the dilution as a crude material and separate, thereby clogging the spray device or causing administration problems.

  Surprisingly, it has been found that these problems can be overcome by the following suspension concentrates of the pyripyropene pesticide compound of formula I. These suspension concentrates have excellent formulation stability, especially against the formation of coarse particles and sedimentation of the active ingredient from the formulation or aqueous dilution.

The present invention also provides
a) 5 to 30 wt%, in particular 6 to 20 wt%, in particular 8 to 15 wt% of the pesticide compound of formula I, based on the total weight of the formulation,
b) 6-20 wt%, in particular 8-17 wt%, in particular 9-15 wt% of an anionic polymer surfactant having a plurality of SO ^3- groups, based on the total weight of the formulation,
c) 0.1 to 10 wt%, in particular 0.5 to 8 wt%, in particular 1 to 5 wt% of nonionic surfactant relative to the total weight of the formulation,
d) of the formula I as defined above, in the form of microparticles suspended in an aqueous liquid, comprising 40-88.9% by weight, in particular 55-85.5 wt%, in particular 65-82 wt% of water, based on the total weight of the formulation The present invention relates to an aqueous pesticide preparation comprising a pyripyropene pesticide compound.

  The term wt%, as used herein, should be understood as weight%.

  It has also been found that the problems associated with aqueous formulations of compounds of formula I can be overcome by the specific crystalline hydrates defined below.

Thus, a further aspect of the present invention is the following 2θ values by X-ray powder diffraction at 25 ° C. and Cu-K _α- ray: 9.7 ± 0.2 °, 10.3 ± 0.2 °, 11.3 ± 0.2 °, 14.0 ± 0.2 °, It relates to a hydrate A of a compound of formula I which exhibits at least four, in particular at least five, or all of the reflections given as 15.5 ± 0.2 °, 16.4 ± 0.2 °, 17.6 ± 0.2 °.

Further, a further aspect of the present invention is the following 2θ values by X-ray powder diffraction at 25 ° C. and Cu-K _α ray: 8.0 ± 0.2 °, 9.5 ± 0.2 °, 10.7 ± 0.2 °, 11.0 ± 0.2 °, At least four of the reflections given as 11.2 ± 0.2 °, 11.7 ± 0.2 °, 14.2 ± 0.2 °, 15.6 ± 0.2 °, 16.5 ± 0.2 °, 17.7 ± 0.2 °, 21.5 ± 0.2 °, in particular at least five, or at least It relates to hydrates B of the compounds of the formula I, showing seven, or at least nine, or all.

Further, a further aspect of the present invention is the following 2θ values by X-ray powder diffraction at 25 ° C. and Cu-K _α ray: 7.5 ± 0.2 °, 9.6 ± 0.2 °, 11.0 ± 0.2 °, 11.7 ± 0.2 °, At least four of the reflections given as 12.1 ± 0.2 °, 12.5 ± 0.2 °, 15.8 ± 0.2 °, 16.3 ± 0.2 °, 17.4 ± 0.2 °, 19.3 ± 0.2 ° and 19.6 ± 0.2 °, in particular at least five, or at least It relates to a hydrate C of a compound of the formula I, showing seven, or at least nine, or all.

FIG. 2 shows an X-ray powder diffraction (XRPD) of Form A obtained from the suspension concentrate of Example 1. FIG. 4 shows an X-ray powder diffraction (XRPD) of Form B. FIG. 4 shows an X-ray powder diffraction (XRPD) of form C.

  Combinations of preferred embodiments with other preferred embodiments are within the scope of the invention.

  The pesticide can be present in the composition of the present invention in any form such as dissolved, suspended or emulsified form. Preferably, the pesticide compound of formula I or II is present in the composition in dissolved or suspended form. In particular, the composition comprising the adjuvant and the pesticide compound of formula I or II is an aqueous composition in the form of a suspension or emulsion, wherein the pesticide compound of formula I or II is It exists in the form or in the form of emulsified droplets containing the pesticidal compound in dissolved form.

  Suitable auxiliaries are all known materials of this class, for example known to the person skilled in the art from Hazen, Weed Technology, 2000, 14, pp. 773-784 “Adjuvants-terminology, classification and chemistry”. Examples are humectants-adjuncts as spreading agents, sticking auxiliaries, humectants or penetrants. Further examples are surfactants (e.g. nonionic, anionic, cationic or ampohoteric), wetting agents, spreading agents, adhesives, humectants, penetrants (e.g. paraffinic or plant derived) Crop oil concentrate, oil that is not phytobland, emulsifiable crop oil crop, vegetable oil concentrate, modified vegetable oil). Definitions and examples of the above terms are given in Hazen (2000).

Preferred examples of adjuvants include their main functional components and are listed in Table 1 based on the brand name of the adjuvant.

  Further preferred examples of adjuvants are the following substances and compositions.

-Sodium dioctylsulfosuccinate, commercially available, for example from the product series Geropon®,
-Commercially available composition, for example of the product series Aerosol®, containing sodium dioctylsulfosuccinate and sodium benzoate (weight ratio of dioctylsulfosuccinate: sodium benzoate is preferably 5: 1-6: 1 is there),
End-capped alkoxylated fatty alcohols and end-capped alkoxylated linear alcohols (preferably ethoxylated and / or butoxylated fatty alcohols and terminators), eg of the product series Plurafac® Is a capped ethoxylated and / or butoxylated linear alcohol)
-Commercially available tributylphenol polyglycol ether with 10 to 15 EO units (e.g. EO means ethylene oxide), e.g. as Sapogenat®
A commercially available polymethylsiloxane modified with polyalkylene oxide, for example of the product series Silwet®,
-Commercially available, for example, of the product series Lutensol®, the formula C _t H _{2t + 5} (-CH ₂ -CH ₂ -O-) _u -H, where t represents the number 11 to 13.5, u Represents a branched alkanol alkoxylate of the number 6 to 25 (preferably 8 to 12 and t and u are average values),
-Betaine,
A polyalkoxylated triglyceride (triglycerides are preferably of plant origin) commercially available, for example of the product series Crovol®,
A commercially available alkoxylated fatty amine, for example of the product series Armoblen®,
-Commercially available, for example, the product series Genapol®, sodium laureth sulfate,
-PEG-10 coconut alcohol, commercially available, for example from the product series Genapol®,
A composition comprising corn syrup, petroleum and nonionic emulsifiers, commercially available, for example of the product series Superb®,
-Brij® 92, containing oleyl alcohol ethoxylate with an average of 2 moles of ethoxylate,
-Adol® 320, including oleyl alcohol
-Priolene® 6910, including oleic acid,
-Turbocharge®, including a proprietary blend of oil and short chain ethoxylates,
-Merge®, including a proprietary blend of oil and short chain ethoxylates,
-Dash®, including a proprietary blend of oil and short chain ethoxylates,
-Silwet® L77, including ethoxylated silicone
-Ethomeen® S12 containing short chain ethoxylated fatty amines,
Hystrene® 9018 with stearic acid.

  Suitable surfactants include aromatic sulfonic acids such as lignosulfonic acid (Borresperse® type, Borregaard, Norway), phenolsulfonic acid, naphthalenesulfonic acid (Morwet® type, Akzo Nobel, USA). And dibutylnaphthalene sulfonic acid (Nekal® type, BASF, Germany), and alkali metal, alkaline earth metal and ammonium salts of fatty acids, alkyl sulfonates and alkylaryl sulfonates, alkyl sulfates, lauryl ether sulfates and fats Alcohol sulfate and sulfated hexadecanol, heptadecanol and octadecanol salts, fatty alcohol glycol ether salts, sulfonated naphthalene and its derivatives and formaldehyde condensates, naphthalene and naphthalene Condensation of sulfonic acid with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctylphenol, octylphenol or nonylphenol, alkylphenyl polyglycol ether, tributylphenyl polyglycol ether, alkylaryl polyether alcohol, isotridecyl alcohol, fat Alcohol / ethylene oxide condensate, ethoxylated castor oil, polyoxyethylene alkyl ether or polyoxypropylene alkyl ether, lauryl alcohol polyglycol ether acetate, sorbitol ester, lignin sulfite waste liquor, as well as proteins, modified proteins, polysaccharides (e.g. methylcellulose), Starch modified with hydrophobic substances, polyvinyl alcohol ( Mowiol® type, Clariant, Switzerland), polycarboxylate (Sokalan® type, BASF, Germany), polyalkoxylate, polyvinylamine (Lupamin® type, BASF, Germany), polyethyleneimine ( Lupasol® type, BASF, Germany), polyvinylpyrrolidone, and copolymers thereof.

  Particularly suitable surfactants are anionic, cationic, nonionic and amphoteric surfactants and polyelectrolytes (nonionic surfactants are preferred). Suitable anionic surfactants are alkali, alkaline earth or ammonium salts of sulfonates, sulfates, phosphates or carboxylates. Examples of sulfonates include alkylaryl sulfonates, diphenyl sulfonates, alpha-olefin sulfonates, fatty acid and oil sulfonates, ethoxylated alkylphenol sulfonates, condensed naphthalene sulfonates, dodecylbenzene and tridecylbenzene sulfonates, naphthalene and alkylnaphthalene sulfonates, Sulfosuccinate or sulfosuccinamate. Examples of sulfates are fatty acids and oils, ethoxylated alkylphenols, alcohols, ethoxylated alcohols, or fatty acid ester sulfates. An example of a phosphate is a phosphate ester. Examples of carboxylates are alkyl carboxylates and carboxylated alcohols or alkylphenol ethoxylates.

  Suitable nonionic surfactants are block polymers, alkoxylates, N-alkylated fatty acid amides, amine oxides, esters or saccharide based surfactants. Examples of alkoxylates are alkoxylated compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters. For the alkoxylation, ethylene oxide and / or propylene oxide, preferably ethylene oxide can be used. Examples of N-alkylated fatty acid amides are fatty acid glucamide or fatty acid alkanolamide. Examples of esters are fatty acid esters, glycerol esters or monoglycerides. Examples of saccharide surfactants are sorbitan, ethoxylated sorbitan, sucrose and glucose esters or alkylpolyglucosides. Suitable block polymers are A-B or A-B-A type block polymers comprising polyethylene oxide and polypropylene oxide blocks, or AB-C type block polymers comprising alkanols, polyethylene oxide and polypropylene oxide. Examples of suitable cationic surfactants are quaternary surfactants, such as quaternary ammonium compounds having one or two hydrophobic groups, or salts of long chain primary amines. Suitable amphoteric surfactants are alkylbetaines and imidazolines. Suitable polyelectrolytes are polyacids or polybases. An example of a polyacid is an alkali salt of polyacrylic acid. Examples of polybases are polyvinylamine or polyethyleneamine.

Suitable penetrants are any customary substances that can improve the penetration of pesticide substances into plants. Preferably, the following mineral oils, vegetable oils, esters of vegetable oils, fatty acid esters having 10-20 carbon atoms in the acid part and 1-10 carbon atoms in the alcohol part, 4-12 in the acid part A saturated or unsaturated dicarboxylic acid ester having 1 to 8 carbon atoms in each alcohol moiety, an aromatic dicarboxylic acid ester having 1 to 8 carbon atoms in each alcohol moiety, and Alkanol alkoxylates are also suitable. Examples of penetrants that can be listed are
-Mineral oil,
-Rapeseed oil, sunflower oil, corn oil, linseed oil, oilseed rape (turnip rape) oil, olive oil, cottonseed oil,
-Rapeseed oil methyl ester, rapeseed oil ethyl ester, rapeseed oil methyl ester, rapeseed oil ethyl ester,
-Ethylhexyl laurate,
-Dibutyl succinate, dibutyl adipate, dibutyl phthalate, and
-Alkanol alkoxylates of formula R--O-(AO) _m --R ¹
(Wherein, R represents a linear or branched alkyl or alkenyl having from 4 to 20 carbon atoms, AO is C ₂ -C ₄ - alkylene oxide groups, i.e. ethylene oxide group (CH ₂ -CH ₂ -O ), Propylene oxide groups (CH (CH ₃ ) —CH ₂ —O or CH ₂ —CH (CH ₃ ) —O), butylene oxide groups (CH (C ₂ H ₅ ) —CH ₂ —O, C (CH ₃ ) ₂ -CH ₂ -O, CH ₂ -C (CH ₃ ) ₂ -O or CH ₂ -CH (C ₂ CH ₅ ) -O), or a mixture of ethylene oxide and propylene oxide or butylene oxide groups, m Represents the number 1 to 30, in particular 2 to 20, and R ¹ represents hydrogen or alkyl having 1 to 4 carbon atoms)
It is.

  In certain embodiments of the invention, the adjuvant comprises at least one nonionic surfactant. For purposes of use with adjuvants, the nonionic surfactant can be used as is or can be used as a solution in a suitable solvent, such as water or a nonpolar solvent. Suitable non-polar solvents include the aforementioned mineral oils, vegetable oils, esters of vegetable oils, fatty acid esters having 10 to 20 carbon atoms in the acid portion and 1 to 10 carbon atoms in the alcohol portion, in the acid portion. Of saturated or unsaturated dicarboxylic acids having 4 to 12 carbon atoms and 1 to 8 carbon atoms in each alcohol moiety, aromatic dicarboxylic acids having 1 to 8 carbon atoms in the alcohol moiety Esters are included. The amount of nonionic surfactant in these solutions can vary from 10 to 80% by weight, in particular from 15 to 50% by weight.

  In these particular embodiments of the invention, the adjuvant comprises at least one nonionic surfactant as the sole surfactant, or a combination thereof with one or more anionic or cationic surfactants. Can be contained. In this particular embodiment, the nonionic surfactant is preferably present in the adjuvant in an amount of at least 50% by weight, based on the total amount of surfactant in the adjuvant.

Of the group of nonionic surfactants, those having at least one poly-C ₂ -C ₄ -alkylene oxide moiety are preferred. A poly-C ₂ -C ₄ -alkylene oxide moiety is a group having the formula O-(AO) _k --R ^x (R ^x is hydrogen, C ₁ -C ₂₀ -alkyl, C ₁ -C ₂₀ - alkyl or benzyl, especially hydrogen, C ₁ -C ₄ - alkyl, C ₁ -C ₄ - alkylcarbonyl, k is an integer 3 to 250, in particular 3 to 100, in particular from 5 to 50, based on ( AO) AO in _k may be the same or different and is selected from ethylene oxide, propylene oxide and butylene oxide, in particular selected from ethylene oxide and mixtures of ethylene oxide and propylene oxide). Among the group of nonionic surfactants having at least one poly-C ₂ -C ₄ -alkylene oxide moiety, the poly-C ₂ -C ₄ -alkylene oxide moiety comprises one or more ethylenoxide moieties and Those that optionally contain one or more propylene oxide moieties and / or butylene oxide moieties are preferred.

Suitable nonionic surfactants having at least one poly-C ₂ -C ₄ -alkylene oxide moiety include, but are not limited to, alcohol alkoxylates, especially C ₆ -C ₂₂ -alkanols. C ₂ -C ₄ - alkoxylates, alkylphenol alkoxylates, in particular C ₆ -C ₂₂ - alkylphenol C ₂ -C ₄ - alkoxylates, amine alkoxylates, especially C ₆ ~C ₂₂ - C ₂ ~ alkylamine C ₄ -alkoxylates, amide alkoxylates, especially C ₆ -C ₂₂ -alkylamides C ₂ -C ₄ -alkoxylates, arylphenol alkoxylates, especially mono-, di- or tristyrylphenol C _2- C ₄ -alkoxylates, alkoxylates of fatty acids or fatty acid esters, in particular C ₆ -C ₂₂ -C ₂ -C ₄ -alkoxylates of fatty acids, C ₆ -C ₂₂ - C fatty acid mono- or diglycerides ₂ -C ₄ - alkoxylates, and _{C 6 ~C 22 - C 2 ~C} 4 fatty acid sorbitan esters - alkoxylate, and block polymers, in particular poly (C ₂ -C ₄ - alkylene oxide ) Block copolymers are included.

Examples of suitable nonionic surfactants having at least one poly-C ₂ -C ₄ -alkylene oxide moiety include, but are not limited to:

End-capped alkoxylated fatty alcohols and end-capped alkoxylated linear alcohols (preferably ethoxylated and / or butoxylated fatty alcohols and terminators), eg of the product series Plurafac® Is a capped ethoxylated and / or butoxylated linear alcohol)
-Commercially available tributylphenol polyglycol ether with 10 to 15 EO units (e.g. EO means ethylene oxide), e.g. as Sapogenat®
A commercially available polymethylsiloxane modified with polyalkylene oxide, for example of the product series Silwet®,
-Commercially available, for example, of the product series Lutensol®, the formula C _t H _{2t + 5} (-CH ₂ -CH ₂ -O-) _u -H, where t represents the number 11 to 13.5, u Represents a branched alkanol alkoxylate of the number 6 to 25 (preferably 8 to 12 and t and u are average values),
A polyalkoxylated triglyceride (triglycerides are preferably of plant origin) commercially available, for example of the product series Crovol®,
A commercially available alkoxylated fatty amine, for example of the product series Armoblen®,
-PEG-10 coconut alcohol, commercially available, for example from the product series Genapol®,
-Brij® 92, containing oleyl alcohol ethoxylate with an average of 2 moles of ethoxylate,
-Turbocharge®, including a proprietary blend of oil and short chain ethoxylates,
-Merge®, including a proprietary blend of oil and short chain ethoxylates,
-Dash®, including a proprietary blend of oil and short chain ethoxylates,
-Silwet® L77, including ethoxylated silicone
-Ethomeen® S12 containing short chain ethoxylated fatty amines,
An alkanol alkoxylate of the formula R--O-(AO) _m --R ¹ as defined above,
-Sylgard® 309 (3- (3-hydroxypropyl) -heptamethyltrisiloxane, ethoxylated acetate (CAS125997-17-3)> 60% from Dow Corning; allyloxypolyethylene glycol monoallyl (monallyl) acetate (CAS27252-87-5) 15-40%, polyethylene glycol diacetate 1-5%),
-Freeway® (Loveland Products, Inc., silicone-polyether copolymer, linear alcohol ethoxylate, propylene glycol, dimethylpolysiloxane),
-Silwet® L-77 (Helena Chemical Company, polyalkylene oxide modified heptamethyltrisiloxane (CAS27306-78-1) 84%, allyloxypolyethylene glycol methyl ether (CAS27252-80-8) 16% ),
-Kinetic (R) Molecular Zippering Action (polydimethylsiloxane modified with polyalkylene oxide, polyoxyethylene-polyoxypropylene copolymer (CAS9003-11-6), polyoxypropylene oleate butyl ether (CAS37281-78-0) ).

Nonionic surfactants having at least one poly-C ₂ -C ₄ -alkylene oxide moiety are preferably polyethoxylated sorbitan fatty acid esters, poly (ethylene oxide-co-propylene oxide) copolymers, especially alkyl-terminated poly ( ethylene oxide - co - propylene oxide) diblock polymer or poly (ethylene oxide - co - propylene oxide) - triblock polymers, and poly -C ₂ -C ₄ - polydimethylsiloxane modified with alkylene oxide, in particular modified polyethylene oxide Polydimethyldisiloxane, as well as mixtures thereof.

In this particular preferred embodiment of the present invention, the nonionic surfactant having at least one poly-C ₂ -C ₄ -alkylene oxide moiety may be the sole nonionic surfactant of the adjuvant. Or, the adjuvant contains a combination of the nonionic surfactant and one or more nonionic surfactants. In this particular embodiment, the nonionic surfactant having at least one poly-C ₂ -C ₄ -alkylene oxide moiety is preferably at least 50% by weight, based on the total amount of surfactant in the adjuvant. Present in the adjunct.

  In one particular embodiment of the invention, the adjuvant comprises at least one silicone adjuvant. For purposes of use in adjuvants, silicone adjuvants can be used as they are, or in combination with them and one or more other adjuvants, particularly with one or more nonionic surfactants. Can be used.

Typical silicone adjuvants are at least one nonionic polydi-C ₁ -C ₄ -alkyl siloxane, especially at least one oligo- or polydi-C ₁ -C ₄ -alkyl siloxane moiety, especially at least one oligo. -Or at least one polydimethylsiloxane having a polydimethylsiloxane moiety. Polydiene -C ₁ -C ₄ - alkyl siloxane moiety has the formula
-Si (R ^Si ) ₂ -O-
Is a group formed from repeating units of
[Wherein R ^Si is C ₁ -C ₄ -alkyl, in particular methyl (= polydimethylsiloxane)]. The oligo- or polydi-C ₁ -C ₄ -alkylsiloxane moiety can be cyclic or acyclic. Oligo- or polydi-C ₁ -C ₄ -alkylsiloxane moieties generally have at least 3 silicon atoms, for example 3 to 100 Si atoms (number average). Oligo- or polydi-C ₁ -C ₄ -alkyl siloxanes, especially polydimethylsiloxane moieties, are nonionic end groups different from methyl, such as OH or longer chain alkyls (e.g. C ₂ -C ₁₀ -alkyl) Or can have C ₂ -C ₁₀ -alkyl substituted by one or two OH groups.

In addition to the at least one oligo- or polydi-C ₁ -C ₄ -alkylsiloxane moiety, the nonionic polydi-C ₁ -C ₄ -alkylsiloxane comprises one or more polar groups, in particular one or more nonionics. A polar group. Suitable nonionic polar groups include, but are not limited to, alkyl and cycloalkyl groups, monosaccharides or oligosaccharides having two or more, for example 2, 3, 4 or 5 hydroxyl groups. Groups are included, as well as poly-C ₂ -C ₄ -alkylene oxide moieties, especially polyethylene oxide moieties.

In a particularly preferred embodiment, the silicone-based adjuvant, poly -C ₂ -C ₄ - polydiene -C modified with alkylene oxide ₁ -C ₄ - alkyl siloxanes, especially poly -C ₂ -C ₄ - alkylene oxide And polydimethylsiloxane modified with polyethylene oxide, in particular. Poly -C ₂ -C ₄ - In siloxanes, poly -C ₂ -C ₄ - - alkylene polydiene -C modified with oxide ₁ -C ₄ alkylene oxide moieties, especially polyethyleneoxide moiety is usually from 5 to 200 pieces In particular 10 to 100 C ₂ -C ₄ -alkylene oxide repeating units, in particular 5 to 200, in particular 10 to 100 ethylene oxide repeating units.

  In this particular embodiment, the silicone adjuvant is preferably present in the adjuvant in an amount of at least 30% by weight relative to the total amount of adjuvant.

Examples of silicone adjuvants are:
-Sylgard® 309 (3- (3-hydroxypropyl) -heptamethyltrisiloxane, ethoxylated acetate (CAS125997-17-3)> 60% from Dow Corning; allyloxypolyethylene glycol monoallyl acetate (CAS27252- 87-5) 15-40%, polyethylene glycol diacetate 1-5%),
-Freeway® (Loveland Products, Inc., silicone-polyether copolymer, linear alcohol ethoxylate, propylene glycol, dimethylpolysiloxane),
-Silwet® L-77 (Helena Chemical Company, polyalkylene oxide modified heptamethyltrisiloxane (CAS27306-78-1) 84%, allyloxypolyethylene glycol methyl ether (CAS27252-80-8) 16% ),
-Kinetic (R) Molecular Zippering Action (polydimethylsiloxane modified with polyalkylene oxide, polyoxyethylene-polyoxypropylene copolymer (CAS9003-11-6), polyoxypropylene oleate butyl ether (CAS37281-78-0) )
It is.

  In a further particularly preferred embodiment, the adjuvant comprises polydimethylsiloxane modified with polyalkylene oxide and poly (ethylene oxide-block-propylene oxide). Examples thereof are commercially available, such as Kinetic® Molecular Zippering Action from Helena.

  In a further particular embodiment of the invention the adjuvant comprises at least one crop oil concentrate. For the purpose of use as an adjunct, the crop oil concentrate can be used as is or as a combination of them with one or more other adjuncts, in particular with one or more nonionic surfactants. Can be used.

  Crop oil concentrate is usually a mixture comprising a nonpolar high boiling organic liquid and at least one surfactant, in particular at least one nonionic surfactant, or at least one nonionic surfactant and at least one. A mixture of two anionic surfactants. Nonpolar high boiling organic liquids suitable for crop oil concentrates include hydrocarbon solvents, especially non-aromatic hydrocarbon solvents such as aliphatic mineral oil, aliphatic petroleum, white oil, and light and heavy paraffinic oils, As well as fatty acid triglycerides such as vegetable oils. In certain embodiments, the crop oil concentrate contains at least one hydrocarbon solvent, a non-aromatic hydrocarbon solvent, and at least one nonionic surfactant. In certain embodiments of the crop oil concentrate, the nonionic surfactant is selected from polyol fatty acid esters, polyoxyethylenated polyol fatty acid esters, alkylphenol ethoxylates and fatty acids, and mixtures thereof. In a particularly preferred embodiment of the crop oil concentrate, the nonionic surfactant is a sorbitan fatty acid ester such as sorbitan mono- or dilaurate ester or sorbitan mono- or dioleate ester, a polyethoxylated sorbitan mono- or dilaurate ester or Selected from polyoxyethylenated sorbitan fatty acid esters, such as polyethoxylated sorbitan mono- or dioleate, and mixtures thereof.

Examples of suitable crop oil concentrates are:
-Agri-dex® (Helena Chemical Co.) (Heavy and light range paraffinic petroleum (CAS64741-88-4, 64741-89-5) 82%, polyol fatty acid esters and polyoxyethylenated polyol fatty acids A mixture of 17% ester),
-Red-Top Mor-Act® adjuvant (Wilbur-Ellis Co., non-phytotoxin paraffinic petroleum 83%, CAS8012-95-1, polyol fatty acid ester and 15% polyethoxylated derivative thereof),
-Herbimax® petroleum-surfactant adjuvant (Loveland Products, Inc., petroleum hydrocarbon 83% (CAS64741-50-0), odorless aliphatic petroleum solvent (CAS64742-89-8), alkylphenol ethoxylate , Tall oil fatty acid)
It is.

  In one particularly preferred embodiment, the adjuvant comprises petroleum and surfactants, such as sorbitan fatty acid esters and polyethoxylated sorbitan fatty acid esters. More preferably, the adjunct (crop oil concentrate) is at least 50 wt% based on the total weight of the adjunct, such as 50-99 wt% or 60-95 wt% petroleum, and up to 50 wt% based on the total weight of the adjunct. %, For example 1-50 wt% or 5-40 wt% of at least one surfactant. Examples are commercially available, such as Agridex® from Bayer Crop Science.

  In a further embodiment of the invention, the composition comprises, in addition to the compound of formula I or II, at least one alkoxylated fatty alcohol, hereinafter also referred to as alkoxylate. The fatty alcohol on which the alkoxylated fatty alcohol is based can be linear or branched. The fatty alcohol on which the alkoxylated fatty alcohol is based has 5 to 36 carbon atoms, preferably 10 to 32 carbon atoms, more preferably 14 to 26 carbon atoms, in particular 15 to 20 carbon atoms. Can have atoms. It is also possible to use a mixture of an alkoxylated fatty alcohol and a different number of carbon atoms in the aliphatic group of the aliphatic alcohol on which the alkoxylated fatty alcohol is based. The fatty alcohol on which the alkoxylated fatty alcohol is based is preferably a linear aliphatic alcohol, in particular a linear aliphatic alcohol having 14 to 22 carbon atoms or 16 to 20 carbon atoms.

In the context of an alkoxylated fatty alcohol, being alkoxylated means that the OH moiety of the aliphatic alcohol has been replaced by a polyoxyalkylene moiety or a polyalkylene oxide moiety, which are synonymous. To do. The context of the present invention, polyoxyalkylene, (the A, alkanediyl, in particular C ₂ -C ₅ - alkanediyl a) alkylene oxide repeating units AO is an aliphatic polyether group is constructed from. In the context of the present invention, the polyoxyalkylene is preferably a poly-C ₂ -C ₅ -alkylene oxide moiety, more preferably a poly-C ₂ -C ₄ -alkylene oxide moiety, especially a poly-C ₂ -C ₃ -alkylene oxide moiety. For example, a polyethylene oxide moiety, a polypropylene oxide moiety, a poly (ethylene oxide-co-propylene oxide) moiety, a poly (ethylene oxide-co-butylene oxide) moiety or a poly (ethylene oxide-co-pentylene oxide) moiety. The number of alkylene oxide repeating units in the polyoxyalkylene group is generally 1-100 or 2-100, preferably 5-40, more preferably 10-30, especially 12-20.

In a preferred embodiment, the alkoxylated fatty alcohol (alkoxylate) is selected from alkoxylated alcohols of formula (A)
R ^a -O- (C _m H _2m O) _x- (C _n H _2n O) _y- (C _p H _2p O) _z -R ^b (A)
[Where
R ^a is C ₅ -C ₃₆ -alkyl, C ₅ -C ₃₆ -alkenyl or mixtures thereof, preferably linear C ₅ -C ₃₆ -alkyl, C ₅ -C ₃₆ -alkenyl or mixtures thereof, in particular linear C ₁₄ -C ₃₆ - alkyl, C ₁₄ -C ₃₆ - alkenyl or mixtures thereof, or a straight chain C ₁₄ -C ₂₆ - alkyl, C ₁₄ -C ₂₆ - alkenyl or mixtures thereof, more preferably a linear C ₁₄ -C ₂₂ -Alkyl or a mixture thereof, in particular straight chain C ₁₆ -C ₂₀ -alkyl or a mixture thereof,
R ^b represents H or C ₁ -C ₁₂ -alkyl, in particular H or C ₁ -C ₄ -alkyl, preferably H or methyl, in particular H;
m, n, p, independently of one another, represent an integer 2-16, preferably 2-5, more preferably 2, 3 or 2 and 3 (especially 2 and 3);
x, y and z each independently represent a number of 0 to 100, preferably a number of 0 to 30, more preferably 0 to 20,
x + y + z corresponds to a value of 1-100, preferably 5-40, more preferably 10-30, in particular 12-20].

R ^a may be linear or branched, and is preferably linear. R ^a may be saturated or unsaturated, and is preferably saturated. R ^a may be substituted or unsubstituted, and is preferably unsubstituted. Preferably R ^a represents straight chain C ₅ -C ₃₆ -alkyl, C ₅ -C ₃₆ -alkenyl or mixtures thereof. In particular, R ^a represents linear C ₁₄ -C ₃₆ -alkyl, C ₁₄ -C ₃₆ -alkenyl or mixtures thereof, in particular linear C ₁₄ -C ₂₆ -alkyl, C ₁₄ -C ₂₆ -alkenyl or mixtures thereof . More preferably, R ^a represents linear C ₁₄ -C ₂₂ -alkyl or a mixture thereof. Particularly preferably, R ^a represents linear C ₁₆ -C ₂₀ -alkyl or mixtures thereof.

R ^b preferably represents H or methyl, in particular H.

  Preferably, m, n and p independently of one another represent an integer 2 to 5, more preferably 2, 3 or 2 and 3 (especially 2 and 3).

  Preferably, x, y, and z each independently represent a number 0 to 30, more preferably 0 to 20. Preferably x + y + z corresponds to the value 5-40, more preferably 10-30, in particular 12-20.

  According to one particular embodiment, alcohol alkoxylates of the formula (A) are used in which m = 2 and the value of x is greater than 0. In this case, this relates to EO type alcohol alkoxylates, in particular alcohol ethoxylates (m = 2; x> 0; y, z = 0) and alcohol alkoxylates in which the EO block is attached to the alcohol moiety. (m = 2; x> 0; y and / or z> 0) belong. Among the alcohol alkoxylates in which the EO block is bonded to the alcohol moiety, in particular, the EO-PO block alkoxylate (m = 2; x> 0; y> 0; n = 3; z = 0), the EO-PeO block Alkoxylate (m = 2; x> 0; y> 0; n = 5; z = 0) and EO-PO-EO block alkoxylate (m, p = 2; x, z> 0; y> 0; n = 3) can be listed. Particularly preferred are EO-PO block alkoxylates (m = 2; x> 0; y> 0; n = 3; z = 0).

Here, EO represents CH ₂ CH ₂ O below. PO represents CH (CH ₃ ) CH ₂ O or CH ₂ CH (CH ₃ ) O. BuO is CH (C ₂ H ₅ ) CH ₂ O, C (CH ₃ ) ₂ CH ₂ O, CH ₂ C (CH ₃ ) ₂ O, CH (CH ₃ ) CH (CH ₃ ) O or CH ₂ CH ( Represents C ₂ H ₅ ) O, and PeO represents (C ₅ H ₁₀ O).

  Preference is given to EO-PO block alkoxylates in which the ratio of EO to PO (x to y) is 10: 1 to 1:10, preferably 1: 1 to 1:12, in particular 1: 2 to 1: 8. It is. In this context, the degree of ethoxylation (value of x) is generally 1-20, preferably 2-15, in particular 2-10, and the degree of propoxylation (value of y) is generally 1-30, preferably 4 ~ 20, in particular 8-16. The overall degree of alkoxylation, ie the sum of EO and PO units, is generally 2-50, preferably 4-30, in particular 6-20. Further preferred are EO-PeO block alkoxylates in which the ratio of EO to PeO (x to y) is 2: 1 to 25: 1, in particular 4: 1 to 15: 1. In this context, the degree of ethoxylation (value of x) is generally 1-50, preferably 4-25, in particular 6-15, and the degree of pentoxylation (value of y) is generally 0.5-20, preferably 0.5. ~ 4, especially 0.5-2. The overall degree of alkoxylation, ie the sum of EO and PeO units, is generally from 1.5 to 70, preferably from 4.5 to 29, in particular from 6.5 to 17.

  According to a further particular embodiment, alcohol alkoxylates of the formula (A) are used in which n = 2, the values of x and y both exceed 0 and z = 0. Also in this case, these are EO type alcohol alkoxylates, but the EO block is attached to the end. These include in particular PO-EO block alkoxylates (n = 2; x> 0; y> 0; m = 3; z = 0) and PeO-EO block alkoxylates (n = 2; x> 0; y> 0; m = 5; z = 0).

  Preference is given to PO-EO block alkoxylates in which the ratio of PO to EO (x to y) is 1:10 to 10: 1, preferably 12: 1 to 1: 1, in particular 2: 1 to 8: 1. It is. In this context, the degree of ethoxylation (value of y) is generally from 1 to 20, preferably from 2 to 15, in particular from 2 to 10. The degree of propoxylation (value of x) is generally from 0.5 to 30, preferably from 4 to 20, in particular from 6 to 16. The overall degree of alkoxylation, ie the sum of EO and PO units, is generally 1.5-50, preferably 2.5-30, in particular 8-20.

  Further preferred are PeO-EO block alkoxylates with a PeO to EO ratio (x to y) of 1:50 to 1: 3, in particular 1:25 to 1: 5. In this context, the degree of pentoxylation (value of x) is generally 0.5-20, preferably 0.5-4, in particular 0.5-2, and the degree of ethoxylation (value of y) is generally 3-50, preferably 4 ~ 25, in particular 5-15. The overall degree of alkoxylation, ie the sum of EO and PeO units, is generally from 3.5 to 70, preferably from 4.5 to 45, in particular from 5.5 to 17.

  In a further particular embodiment, alcohol alkoxylates of the formula (A) are used in which the values of x, y and z are all greater than zero. These include in particular PeO-EO-PO block alkoxylates (m = 5; x> 0; n = 2; y> 0; m = 3; z> 0).

In one particularly preferred embodiment, the alkoxylate is
R ^a represents linear C ₁₂ -C ₂₂ -alkyl, in particular linear C ₁₀ -C ₂₀ alkyl or mixtures thereof,
R ^b represents H or C ₁ -C ₄ -alkyl, preferably H or methyl, in particular H,
m, n and p each independently represent an integer 2 to 5, preferably 2 to 3,
x, y and z each independently represent a number 0 to 50,
x + y + z corresponds to a value of 5-50, preferably 8-25,
Selected from alkoxylated alcohols of formula (A).

  The wetting power by dipping the alkoxylate is usually at least 120 seconds, preferably at least 180 seconds, in particular at least 220 seconds. The wetting power is usually analyzed according to DIN 1772 at 1 g / L in 2 g / l sodium carbonate at room temperature.

  The surface tension of the alkoxylate is usually at least 30 mN / m, preferably at least 31 mN / m, in particular at least 32 mN / m. Furthermore, the surface tension is preferably 30 to 40 mN / m, in particular 30 to 35 mN / m. The surface tension can be analyzed according to DIN 14370 at 1 g / L at room temperature.

  Preferably, the alkoxylate has a wetting power by immersion of at least 120 seconds and a surface tension of at least 30 mN / m. More preferably, the alkoxylate has a wetting power by immersion of at least 180 seconds and a surface tension of 30-40 mN / m.

  Alkoxylates are known and can be prepared by known methods such as WO98 / 35553, WO00 / 35278 or EP0 681 865. Many alkoxylates are, for example, Atplus (registered trademark) 242 from Croda, Atplus (registered trademark) 245, Atplus (registered trademark) MBA 1303, Plurafac (registered trademark) LF type from BASF SE, Agnique from Cognis ( (Registered trademark) BP 24-24, Agnique (registered trademark) BP 24-36, Agnique (registered trademark) BP 24-45, Agnique (registered trademark) BP 24-54, Agnique (registered trademark) BP24-52R Yes.

  Preferred compositions according to the invention (preferably in the form of emulsion concentrates) are usually at least 10 wt% alkoxylates, for example 10 to 70 wt%, preferably at least 15 wt%, in particular 15 to 50 wt% alkoxy, relative to the composition. Includes rate.

  In preferred compositions of the present invention, an alkoxylated fatty alcohol (alkoxylate) or a mixture of various alkoxylated alcohols can be the sole adjuvant. However, it is also preferred if the alkoxylated fatty alcohol, in particular the alkoxylated fatty alcohol of the formula A, is combined with various adjuvants. In preferred compositions of the invention (preferably in the form of emulsion concentrates) comprising at least one alkoxylated fatty alcohol and at least one different auxiliary agent, the total amount of auxiliary agent is generally at least relative to the composition. 10 wt%, for example 10 to 70 wt%, preferably at least 15 wt%, in particular 15 to 50 wt%.

  In preferred compositions of the invention (e.g. in the form of an emulsion concentrate or tank mix) comprising at least one alkoxylated fatty alcohol and at least one auxiliary agent different therefrom, the alkoxylated fatty alcohol (s) and The weight ratio of at least one auxiliary agent different from it is generally from 1:10 to 10: 1, in particular from 5: 1 to 1: 5 or from 3: 1 to 1: 3.

  The composition of the present invention can also contain auxiliary agents customary in agrochemical formulations. The auxiliaries used depend on the particular application form and the active substance, respectively. Examples of suitable auxiliaries are solvents, solid carriers, dispersants or emulsifiers (such as further solubilizers, protective colloids, surfactants and adhesives), organic and inorganic thickeners, disinfectants, antifreeze agents, Foams, where appropriate colorants and tackifiers or binders (eg for seed treatment formulations).

  Suitable solvents are water, organic solvents such as medium to high boiling mineral oil fractions, such as kerosene or diesel oil, as well as coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, For example, toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalene or derivatives thereof, alcohols such as methanol, ethanol, propanol, butanol and cyclohexanol, ketones such as glycol, cyclohexanone and gamma-butyrolactone, fatty acid dimethylamide, fatty acid and fatty acid Esters, as well as strong polar solvents such as amines such as N-methylpyrrolidone.

  Solid supports are inorganic earths such as silicates, silica gel, talc, kaolin, limestone, lime, chalk, red clay, ocher, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, For example, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, urea, and products of plant origin such as cereal meal, tree bark meal, wood flour and nutshell meal, cellulose powder As well as other solid supports.

  Suitable surfactants (wetting agents, tackifiers, dispersants or emulsifiers) are aromatic sulfonic acids such as ligninsoulfonic acid (Borresperse® type, Borregard, Norway) phenol sulfonic acid, naphthalene sulfone. Acids (Morwet® type, Akzo Nobel, USA), dibutylnaphthalenesulfonic acid (Nekal® type, BASF, Germany), and alkali metal, alkaline earth metal and ammonium salts of fatty acids, alkyl Sulfonates, alkylaryl sulfonates, alkyl sulfates, lauryl ether sulfates, fatty alcohol sulfates, and sulfated hexadecanolate, heptadecanolate and octadecanolate, sulfated fatty alcohol glycol ethers, and also naphthalene or naphthalenesulfonic acid, phenol And formaldehyde condensates, polyoxyethylene octylphenyl ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenyl polyglycol ether, tributylphenyl polyglycol ether, tristearyl phenyl polyglycol ether, alkylaryl polyether alcohol, alcohol and fat Alcohol / ethylene oxide condensate, ethoxylated castor oil, polyoxyethylene alkyl ether, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol ester, lignin sulfite waste liquor, as well as proteins, modified proteins, polysaccharides (eg methylcellulose) Modified hydrophobic starch, polyvinyl alcohol (Mowi ol® type, Clariant, Switzerland), polycarboxylate (Sokolan® type, BASF, Germany), polyalkoxylate, polyvinylamine (Lupasol® type, BASF, Germany), polyvinylpyrrolidone, As well as its copolymers.

  Examples of thickeners (i.e. compounds that impart modified fluidity to the formulation, i.e., a high viscosity in the stationary state and a low viscosity during stirring) are polysaccharides, and organic and inorganic clays, For example, xanthan gum (Kelzan®, CP Kelco, USA), Rhodopol® 23 (Rhodia, France), Veegum® (RT Vanderbilt, USA) or Attaclay® (Engelhard Corp., NJ , USA). Bactericides can be added to preserve and stabilize the formulation. Examples of suitable fungicides are those based on dichlorophen and benzyl alcohol hemiformal (Proxel (R) from ICI or Acticide (R) RS from Thor Chemie and Kathon (R) from Rohm & Haas ) MK), and those based on isothiazolinone derivatives such as alkyl isothiazolinones and benzisothiazolinones (Acticide® MBS from Thor Chemie). Examples of suitable antifreeze agents are ethylene glycol, propylene glycol, urea and glycerin. Examples of antifoaming agents are silicone emulsions (e.g. Silikon® SRE, Wacker, Germany or Rhodorsil®, Rhodia, France, etc.), long chain alcohols, fatty acids, fatty acid salts, organofluorine compounds and their It is a mixture. Suitable colorants are low water soluble pigments and water soluble dyes. Examples listed are: Rhodamine B, CI Pigment Red 112, CI Solvent Red 1, Pigment Blue 15: 4, Pigment Blue 15: 3, Pigment Blue 15: 2, Pigment Blue 15: 1, Pigment Blue 80, Pigment Yellow 1, Pigment Yellow 13, Pigment Red 112, Pigment Red 48: 2, Pigment Red 48: 1, Pigment Red 57: 1, Pigment Red 53: 1, Pigment Orange 43, Pigment Orange 34, Pigment Orange 5, Pigment Green 36, Pigment Green 7, Pigment White 6, Pigment Brown 25, Basic Purple 10, Basic Purple 49, Acid Red 51, Acid Red 52, Acid Red 14, Acid Blue 9, Acid Yellow 23, Basic Red 10, and Basic Red 108. Examples of tackifiers or binders are polyvinyl pyrrolidone, polyvinyl acetate, polyvinyl alcohol and cellulose ether (Tylose®, Shin-Etsu, Japan).

  Powders, diffusion materials and fines are mixed or ground simultaneously with each active compound, which is a compound present in the composition of the invention, and, if appropriate, further active substances together with at least one solid carrier. Can be prepared. Granules, such as coated granules, impregnated granules and homogeneous granules, can be prepared by combining the active substance with a solid carrier. Examples of solid carriers are inorganic earths such as silica gel, silicate, talc, kaolin, attaclay, limestone, lime, chalk, red clay, ocher, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide , Ground synthetic materials, for example fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, urea, and products of plant origin such as flour, bark flour, wood flour and nutshell powder, cellulose powder, and other solid carriers It is.

  Examples of formulation types are:

1. Types of compositions diluted with water
i) Water-soluble concentrate (SL, LS)
10 parts by weight of the active substance (eg insecticide A) is dissolved in 90 parts by weight of water or a water-soluble solvent. As an alternative, wetting agents or other auxiliaries are added. The active substance dissolves when diluted with water. A formulation having an active substance content of 10% by weight is thus obtained.

ii) Dispersible concentrate (DC)
20 parts by weight of the active substance (eg insecticide A) is dissolved in 70 parts by weight of cyclohexanone by adding 10 parts by weight of a dispersant, for example polyvinylpyrrolidone. Dilute with water to obtain a dispersion. The content of active substance is 20% by weight.

iii) Emulsifiable concentrate (EC)
15 parts by weight of active substance (eg insecticide A) is dissolved in 75 parts by weight of xylene by adding calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight). Dilute with water to obtain an emulsion. The composition has an active substance content of 15% by weight.

iv) Emulsions (EW, EO, ES)
25 parts by weight of active substance (eg insecticide A) is dissolved in 35 parts by weight of xylene by adding calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight). This composition is introduced into 30 parts by weight of water using an emulsifier (Ultraturrax) to produce a homogeneous emulsion. Dilute with water to obtain an emulsion. The composition has an active substance content of 25% by weight.

v) Suspension (SC, OD, FS)
In a stirred ball mill, 20 parts by weight of active substance (e.g. Insecticide A) is pulverized by adding 10 parts by weight of a dispersant and wetting agent and 70 parts by weight of water or an organic solvent to give a fine activity. A suspension of material is obtained. Dilution with water gives a stable suspension of the active substance. The active substance content in the composition is 20% by weight.

vi) Water-dispersible granule and water-soluble granule (WG, SG)
50 parts by weight of active substance (e.g. Insecticide A) is pulverized with addition of 50 parts by weight of dispersant and wetting agent, and technical appliances (e.g. extruders, spray towers, fluidized beds) are used. Use as a granule wettable powder or water-soluble granule. Dilution with water gives a stable dispersion or solution of the active substance. The composition has an active substance content of 50% by weight.

vii) Water-dispersible powder and water-soluble powder (WP, SP, SS, WS)
75 parts by weight of active substance (eg pesticide A) is ground in a rotor stator mill with the addition of 25 parts by weight of dispersant, wetting agent and silica gel. Dilution with water gives a stable dispersion or solution of the active substance. The active substance content in the composition is 75% by weight.

viii) Gel (GF)
In a stirred ball mill, add 20 parts by weight of active substance (for example, insecticide A), add 10 parts by weight of dispersant, 1 part by weight of gelling agent wetting agent and 70 parts by weight of water or organic solvent. To obtain a fine suspension of the active substance. Dilution with water gives a stable suspension of the active substance, whereby a composition containing 20% (w / w) of active substance is obtained.

2. Types of compositions applied without dilution
ix) dustable powder (DP, DS)
5 parts by weight of active substance (eg insecticide A) is pulverized and mixed well with 95 parts by weight of finely divided kaolin. This gives a powder composition having an active substance content of 5% by weight.

x) Granules (GR, FG, GG, MG)
0.5 part by weight of active substance (eg insecticide A) is pulverized and combined with 99.5 parts by weight of carrier. Current methods are extrusion, spray drying or fluidized bed. This gives granules to be applied undiluted with an active substance content of 0.5% by weight.

xi) ULV solution (UL)
10 parts by weight of the active substance (eg insecticide A) is dissolved in 90 parts by weight of an organic solvent, for example xylene. This gives a composition to be applied undiluted with an active substance content of 10% by weight.

  Agrochemical formulations generally comprise between 0.01 and 95% by weight of active substance, preferably between 0.1 and 90%, most preferably between 0.5 and 90%. Insecticide A is used in a purity of 90% to 100%, preferably 95% to 100% (according to NMR spectrum).

  The compositions of the invention can be used as they are or in the form of their agrochemical formulations, for example directly sprayable solutions, powders, suspensions, dispersions, emulsions, oil dispersions, pastes, powders production Can be used in the form of products, diffusion materials or granules, using spraying, atomizing, micronizing, diffusion, brushing, dipping or pouring. The application form depends entirely on the intended purpose, and in each case it is intended to ensure a distribution in which the compounds present in the composition of the invention can be the finest.

  Aqueous application forms can be prepared from emulsion concentrates, pastes or wettable powders (sprayable powders, oil dispersions) by adding water thereto. To prepare emulsions, pastes or oil dispersions, the substance can be homogenized in water as is or dissolved in oil or solvent and using a wetting agent, tackifier, dispersant or emulsifier. Can do. Alternatively, it is possible to prepare a concentrate composed of active substance, wetting agent, tackifier, dispersant or emulsifier and, where appropriate, a solvent or oil, such concentrate being diluted with water. Suitable for doing.

  The active substance concentration of ready-to-use preparations can vary over a relatively wide range. In general, the concentration is from 0.0001 to 10%, preferably from 0.001 to 1% by weight of the compound of the composition of the invention.

  The compounds of the composition of the present invention can also be used successfully in the ultra-low volume method (ULV), it is possible to apply compositions containing more than 95% by weight of active substance, or even additives It is also possible to apply the active substance without it.

  Various types of oils, wetting agents, adjuvants, herbicides, fungicides, other pesticides or fungicides can be added to the active compounds just before use, if appropriate (tank mix). These agents can be admixed with the compounds of the composition of the invention in a weight ratio of 1: 100 to 100: 1, preferably 1:10 to 10: 1.

  The compositions of the present invention may also contain fertilizers such as ammonium nitrate, urea, potash and superphosphate, substances harmful to plants and plant growth regulators and safeners. These can be used sequentially or in combination with the aforementioned compositions and, if appropriate, can also be added only shortly before use (tank mix). For example, the plant (s) can be sprayed with the composition of the present invention either before or after treatment with the fertilizer.

  The compounds of the composition of the present invention can be used individually to prepare the composition of the present invention, or may already be partially or completely mixed with each other. The compounds of the composition of the present invention can be packaged and further used as a combination composition such as a kit of parts. In one embodiment of the present invention, the kit of parts comprises a) a pesticide and b) an adjuvant as separate components for use in combination. The kit can include one or more components, including all, that can be used to prepare a subject pesticide composition. In embodiments where more than two components are provided as a kit, the components may already be combined together, as such, in a single container such as a vial, bottle, can, pouch, bag or small container. Packaged in. In other embodiments, two or more components of the kit can be packaged separately, i.e., not pre-formulated. Thus, the kit can include one or more separate containers, such as vials, cans, bottles, pouches, bags or small containers, each container containing a separate component for the agrochemical composition. In both forms, the components of the kit are applied separately from the additional components or together with the additional components or as a component of the combination composition of the invention for preparing the composition of the invention. can do.

  The user applies the composition of the present invention, usually from a predosage device, a shoulder sprayer, a spray tank or a spray plane. Here the pesticidal composition is composed of water and / or buffer up to the desired application concentration, and if appropriate, further auxiliaries can be added and are therefore ready to use. A spray solution or an agrochemical composition is obtained. Usually, 50-500 liters of ready-to-use spray solution, preferably 100-400 liters, is applied per hectare of an agriculturally useful area.

  The invention further relates to a method for protecting a plant from attack or parasitism by insects, ticks or nematodes, said method comprising a plant or soil or water on which the plant grows and a pesticide effective amount of the invention. Contacting with the composition.

  The present invention further relates to a method for controlling insects, spiders or nematodes, said methods comprising insects, ticks or nematodes or their food supply, habitat, hotbed or their location and a pesticidally effective amount. Contacting with the composition of the present invention.

  The composition of the present invention exhibits outstanding effects on the following animal pests of the eye (eg insects, mites or nematodes).

Insects from Lepidoptera, such as Agrotis ypsilon, Agrotis segetum, Alabama argillacea, Antiticia gemmatalis, Argyresia gythia conjugella, Autographa gamma, Bupalus piniarius, Cacoecia murinana, Capua reticulana, Cheimatobia brumata, Ciferatoura um ), Choristoneura occidentalis, Kirphis unipuncta, Cydia pomonella, Dendrolimus pini, Diaphania nitidalis, Diaphania nitidalis Diatraea grandiosella, Earias insulana, Elasmopalpus lignosellus, Eupoecilia ambiguella, Evetria bouliana sube, nea・ Geleria mellonella, Grapholitha funebrana, Grapholitha molesta, Heliothis armigera, Heliothis virescens, Heliothis zea, Heliothis ze (Hellula undalis), Hibernia defoliaria, Hyphantria cunea, Hyponomeuta malinellus, Keiferia lycopersicella, Lambina physic Lambdina fiscellaria, Laphygma exigua, Leucoptera coffeella, Leucoptera scitella, Lithocolletis blancardella, Lobesia botrana Loxostege sticticalis, Lymantria dispar, Lymantria monacha, Lyonetia clerkella, Malacosoma neustria, Mamestra brassiae, Mamestra brasse Orgyia pseudotsugata, Ostrinia nubilalis, Panoris flammea, Pectinophora gossypiella, Peridroma saucia, Farrera cereal (Phalera bucephala), Phthhorimaea operculella, Phyllocnistis citrella, Pieris brassicae, Plathypena scabra, Plutella xylostella (ella) Inclusions (Pseudoplusia includens), Rhyacionia frustrana, Scrobipalpula absoluta, Sitotroga cerealella, Sparganothis pilleriana, pods, pods・ Litoralis (Spodoptera littoralis), Spodoptera litura (Spodoptera litura), Thaumatopoea pityocampa, Tortrix viridana (Tortrix viridana), Trichoplusia ni (Trichoplusi) a ni) and Zeiraphera canadensis,
Coleoptera (Coleoptera), for example, Agrilus sinuatus, Agriotes lineatus, Agriotes obscurus, Amphimallus russtitials, Amphimallus solstitial dispar), Anthonomus grandis, Anthonomus pomorum, Aphthona euphoridae, Athous haemorrhoidalis, Atomaria linearis B piniperda, Britofaga undata, Bruchs rufimanus, Bruchus pisorum, Bruchs lentis, Byctiscus betulae, Byctiscus betulae, Byctiscus betulae Cassida nebulosa, Cerotoma trifurcata, Cetonia aurata, Sortlinks asimilis, Sortlinks napi (Ceuthorrhynchus napi), Kaetokunema cnito s Conoderus vespertinus), Crioceris asparagi, Ctenicera spp., Diabrotica longicornis, Diabrotica semipunctata, Diabrotica semipunctata 12-rot ica Diabrotica speciosa, Diabrotica virgifera, Epilacachna varivestis, Epitrix hirtipennis, Eutinoboth brushriensis (Eutinobothr) us brasiliensis), Hyrobius abietis, Hipera brunneipennis, Hypera postica, Ips typographus, Lema bilineata, Lema bilineata, Lema bilineata melanopus), Leptinotarsa decemlineata, Limonius californicus, Lissorhoptrus oryzophilus, Melonotes communis, Melonetos communis ), Melolontha melolontha, Oulema oryzae, Otiorrhynchus sulcatus, Otiorrhynchus ovatus, Faedon coha leon Phyllobius pyri, Phyllotreta chrysocephala, Phyllophaga spp., Phyllopertha horticola, Phyllotreta nemorum (Phyllotreta nemorum) Popylia japonica, Sitona lineatus and Sitophilus granaria,
Flies, mosquitoes (Diptera), e.g., Aedes aegypti, Aedes albopictus, Aedes vexans, Anastrepha ludens, Anofeles macripis Anopheles maculipennis), Anopheles crucians, Anopheles albimanus, Anopheles gambiae, Anopheles freeborni, Anopheles leucos leucos leucos Anopheles minimus, Anopheles quadrimaculatus, Calliphora vicina, Ceratitis capitata, Chrysomya bezziana, Chrysomya bea Chrysomya macellaria, Chrysops discalis, Chrysops silacea, Chrysops atlanticus, Cochliomyia hominivorx, Cochliomyia hominivor Cordylobia anthropophaga, Culicoides furens, Culex pipiens, Culex nigripalpus, Culex quinquefasciatus, Culex quinquefasciatus , Criseta inornata, Criseta melanura, Dacus cucurbitae, Dacus oleae, Dasineura brassicae, Delia antique Delia antique, Delia coarctata, Delia platura, Delia radicum, Dermatobia hominis, Fania canicularis, Geomiza trypuntata (Geomyza Tripunctata), Gasterophilus intestinalis, Glossina morsitans, Glossina palpalis, Glossina fuscipes, Glossina tachinoides (ides), Glossina tachinoides (ides) Iritans (Haematobia irritans), Haplodiplosis equestris, Hippelates spp., Hylemyia platura, Hypoderma lineens, Hypoderma lineens, Leopconosto rr・ Swallow (Li riomyza sativae), Liriomyza trifolii, Lucilia caprina, Lucilia cuprina, Lucilia sericata, Lycoria pectoralisonia, mansonia ), Mayetiola destructor, Musca domestica, Muscina stabulans, Oestrus ovis, Opomyza florum, Ocinera frit (Oscinella frit) , Pegomya hysocyami, Phorbia antiqua, Phorbia brassicae, Phorbia coarctata, Phlebotomus argentipes, Psolofora colentie, Psolofora columbiae Pousilla Rosae (Psila rosae), Psorophora discolor, Prosimulium mixtum, Rhagoletis cerasi, Rhagoletis pomonella, saricoha sagais (Sarcophaga spp.), Simulium vittatum, Stomoxys calcitrans, Tabanus bovinus, Tabanus atratus, Tabanus lineola and Tabanus lineola (Tabanus similis), Tipula oleracea and Tipula paludosa,
Thrips (Thysanoptera), e.g., Dichromothrips corbetti, Dichromothrips spp., Frankliniella fusca, Frankliniella occidentalis, ccalilinella Frankliniella tritici, Scirtothrips citri, Tryps oryzae, Tryps palmi and Thrips tabaci,
Termites (Isoptera), e.g., Carotermes flavicollis, Leucotermes flavipes, Heterotermes aureus, Reticulitermes flavipes, Reticulitermes flavipes・ Birginics (Reticulitermes virginicus), Reticulitermes lucifugus (Reticulitermes lucifugus), Termes natalensis and Copttotermes formosanus,
Cockroaches (Blattaria-Blattodea), e.g., Blattella germanica, Blattella asahinae, Periplaneta americana, Periplaneta japonica, Periplaneta japonica, Periplaneta japonica brunnea), Periplaneta fuligginosa, Periplaneta australasiae, and Blatta orientalis,
Hemiptera (Hemiptera), e.g., Acrosternum hilare, Blissus leucopterus, Cyrtopeltis notatus, Dysdercus tusula, tuss Dysdercus intermedius, Eurygaster integriceps, Euschistus impictiventris, Leptogross phyllopus, L Lygus pratensis, Nezara viridula, Piesma quadrata, Solubea insularis, Thyanta perditor, Acrythosiphon onobrychis, Acrythosiphon onobrychis Kiss (Adelges laricis), Aphidula nasturtii, Aphis fabae, Aphis forbesi, Aphis pomi, Aphis gossypii, Aphis gossypii, Aphis gossypii Aphis grossulariae, Aphis schneideri, Aphis spiraecola, Aphis sambuci, Acyrthosiphon pisum, Aulacorthum solumi Foli (Bemisia argentifolii), Brachycaudus cardui, Brachycaudus helichrysi, Brachycaudus persicae, Brachycaudus prunecola Capitophorus horni, Cerosipha gossypii, Chaetosiphon fragaefolii, Cryptomyzus ribis, Dreyfusia nordmannianae, siaice psi Dysaphis radicola, Dysaulacorthum pseudosolani, Dysaphis plantaginea, Dysaphis pyri, Empoasca fabae, Hiropus lactucae), Macrosiphum avenae, Macrosiphum euphorbiae, Macrosiphon rosae, Megoura viciae, Melanafis pirarius (Mel) anaphis pyrarius), Metopolophium dirhodum, Myzus persicae, Myzus ascalonicus, Myzus cerasi, Myzus varians, Naznis varians (Nasonovia ribis-nigri), Nilaparvata lugens, Pemphigus bursarius, Perkinsiella saccharicida, Horodon humili, Psila mali, sila mali Psylla piri, Rhopalomyzus ascalonicus, Rhopalosiphum maidis, Rhopalosiphum padi, Rhopalosiphum inserta, Rhopalosiphum inserta, Rhopalosiphum inserta, Rhopalosiphum (Sappaphis mali) Minum (Schizaphis graminum), Schizoneura lanuginosa, Sitobion avenae, Trialeurodes vaporariorum, Toxoptera aurantiiani, Toxoptera aurantiian Cetex lectularius, Cimex hemipterus, Reduvius senilis, Triatoma spp. And Arilus critatus,
Ants, bees, bees, bees (Hymenoptera), for example, Athalia rosae, Atta cephalotes, Atta capiguara, Atta laevigata Atta robusta, Atta sexdens, Atta texana, Crematogaster spp., Hoplocampa minuta, Hoplocampa testudine test , Monomorium pharaonis, Solenopsis geminata, Solenopsis invicta, Solenopsis richteri, Solenopsis xyloni , Pogoonomyrmex calfornicus ifornicus), Pheidole megacephala, Dasymmuta occidentalis, Bombus spp., Vespula squamosa, Paravespura vulgaris (Paravespula vulgaris) Paravespula pennsylvanica, Paravespula germanica, Dolichovespula maculata, Vespa crabro, Polistes rubiginosa, Camponotus lines humline ),
Crickets, grasshoppers, locusts (Orthoptera), for example, Acheta domestica, Gryllotalpa gryllotalpa, Locusta migratoria, Melanoplus bivittatus Melanoplus femurrubrum, Melanoplus mexicanus, Melanoplus sanguinipes, Melanoplus spretus, Nomadacris septa Na (Schistocerca americana), Sistocerca gregaria, Dokiostaurus maroccanus, Tachycines asynamorus, Oedaleus senegalensis, Zoegalus Egatsusu (Zonozerus variegatus), hieroglyph vinegar Daganenshisu (Hieroglyphus daganensis), Kurausaria-Angurifera (Kraussaria angulifera), Kariputamusu-Itarikusu (Calliptamus italicus), Korutoisetesu Termini Blow (Chortoicetes terminifera), and Rokusutana-Parudarina (Locustana pardalina),
Spiders such as arachnids (Acarididae), e.g. Argasidae, Ixodidae, and Sarcoptidae, e.g. Amblyomma americanum, Amblyomma variegatum Ambryomma maculatum, Argas persicus, Boophilus annulatus, Boophilus decoloratus, Boophilus microplus, dermacentrum centrum Dermacentor andersoni, Dermacentor variabilis, Hyalomma truncatum, Ixodes ricinus, Ixodes rubicundus, Ikades rubicundus des scapularis, Ixodes holocyclus, Ixodes pacificus, Ornithodorus moubata, Ornithodorus hermsi, Ornithodorus honnitus ), Otobius megnini, Dermanyssus gallinae, Psoroptes ovis, Rhipicephalus sanguineus, Rhipicephalus tusguitus Sarcoptes scabiei, as well as Eriophyidae, eg, Aculus schlechtendali, Phyllocoptrata oleivora And Eriophyes sheldoni; Tarsonemidae spp., E.g. Phytonemus pallidus and Polyphagotarsonemus latus; P. For example, Brevipalpus phoenicis; Tetranychidae spp., For example, Tetranychus cinnabarinus, Tetranychus kanzawai, Tetranychus pacific, Tetranychus telarius and Tetranychus urticae, Panonychus ulmi, Panonychus citri, and Oligonychus pratensis; Araneida For example, Latrodextus Ma Chest of drawers (Latrodectus mactans), Rokusoseresu-Rekurusa (Loxosceles reclusa),
Fleas (Siphonaptera), e.g. Ctenocephalides felis, Ctenocephalides canis, Xenopsylla cheopis, Pulex irritans, Pulex irritans・ Tunga penetrans and Nosopsyllus fasciatus,
Spots, spotted (Thysanura), such as Lepisma saccharina and Thermobia domestica,
Centipedes (Chilopoda), for example, Scutigera coleopterata
optrata),
Millipede (Diplopoda), for example, Narceus spp.
Earwigs (Dermaptera), for example, forficu
la auricularia),
Lice (Phthiraptera), e.g. Pediculus humanus capitis, Pediculus humanus corporis, Pthirus pubis, Haematopinus euryus Switzerland (Haematopinus suis), Linognathus vituli, Bovicola bovis, Menopon gallinae, Menacanthus stramineus and Solenopotes capoles capoles
Plant parasitic nematodes such as root-knot nematodes, Meloidogyne arenaria, Meloidogyne chitwoodi, Meloidogyne exigua, Meloidogyne hapla, Meloidogyne hapla , Meloidogyne javanica and other Meloidogyne species; cyst nematodes, Globodera rostochiensis, Globodera pallida, Globodera tabacum (Globa tabacum) Other Globodera species, Heterodera avenae, Heterodera glycines, Heterodera schachtii, Heterodera trifolii, and other heterodes Heterodera species; Humpworm nematodes, Anguina funesta, Anguina tritici and other Anguina species; Stem and leaf nematodes, Aplencoides Bessey (Aphelenchoides besseyi), Aphelenchoides fragariae, Apelenchoides ritzemabosi, and other species of the genus Aphelenchoides (Aphelenchoides species); the sting nematode, the genus Veronimus longonus Belonolaimus species; Pine nematodes, Bursaphelenchus xylophilus and other Bursaphelenchus species; Ring nematodes, Criconema species, Criconemella species ), Criconemoides specie s), and Mesocriconema species; stem and bulb nematodes, Ditylenchus destructor, Ditylenchus dipsaci, Ditylenchus myceliophagus and other species of Ditylenchus myceliopharenx (Ditylenchus species); awl nematodes, Dolichodorus species; spiral nematodes, Helicotylenchus dihystera, Helicocotlenchus multicinctus and other Helicotylenchus species, Rotylenchus robustus, and other Rotylenchus species; helminthic nematodes, Hemicycliophora species and Hemicliconophora species Hemicriconemoides species; Hill Hirshmanniella species; lance nematodes, Hoplolimus columbus, Hoplolimus galeatus, and other Hoplolimus species; pseudoroot-knot nematodes, nacobus・ Abelans (Nacobbus aberrans) and other Nacobbus species; needle nematodes, Longidorus elongates and other Longidorus species; pin nematodes, Paratylenchus species; Lesion nematodes, Pratylenchus brachyurus, Pratylenchus coffeae, Pratylenchus curvitatus, Pratylenchus praus Negrektus (Pratylencus neglec tus), Pratylenchus penetrans, Pratylenchus scribneri, Pratylenchus vulnus, Pratylenchus zeae, and other Platylenchus species; Cocopyrus (Radinaphelenchus cocophilus) and other Radinaphelenchus species; perforated nematodes, Radopholus similis and other Radopholus species; nephrogenic nematodes, Rochulencruz Rotylenchulus reniformis and other Rotylenchulus species; Scutellonema species; stubby root nematodes, Trichodorus primitives and other Trichodrus species Species (Trichodorus species); Paratricodorus Minor (Paratrichodorus minor) and other Paratricrichodorus species; stunt nematodes, Tylenchorhynchus claytoni, Tylenchorhynchus dubius and other Turenco Tylenchorhynchus species and Merlinius species; citrus nematodes, Tylenchulus semipenetrans and other Tylenchulus species; dagger nematodes Xiphinema americanum, Xiphinema index, Xiphinema diversicaudatum and other Xiphinema species; and other plant parasitic nematode species.

  The compositions of the present invention can be applied to any and all developmental stages of pests such as eggs, larvae, pupae and adults. The pest can be controlled by contacting the targeted pest, its food supply, habitat, hotbed or location thereof with a pesticide effective amount of the composition of the present invention. “Location” means a plant, plant propagation material (preferably seed), soil, area, material or environment in which a pest can grow or can grow.

  In general, a “pesticide effective amount” is observable for growth, including the effect of necrotic, killing, delaying, preventing and removing, destroying or otherwise reducing the occurrence and activity of animal pests. It means the amount of the composition of the present invention necessary to achieve the effect. The pesticidally effective amount can vary for the various compositions used in the present invention. The pesticidally effective amount of the composition will also vary according to general conditions such as the desired pesticidal effect and duration, weather, target species, location, application method, and the like.

  The composition of the present invention treats animal pests or plants, plant propagation materials (preferably seeds), materials or soil to be protected from pesticide attacks with a pesticide effective amount of active compound. Used by. This application can be carried out both before and after an infection of the pest material, plant or plant propagation material (preferably seed) occurs.

  Preferably, the composition according to the invention is obtained by foliar treatment of an animal pest, or a plant or soil to be protected from pesticidal attack, with a pesticidally effective amount of active compound. Used. Also herein, this application can be performed both before and after the plant infection by the pest occurs.

  In a method against animal pests (insects, ticks or nematodes), the application rate of the composition of the present invention is between 0.1 g / ha and 10000 g / ha, preferably 1 g, depending on the type of compound and the desired effect. / ha to 5000 g / ha, more preferably 20 to 100 g / ha, most preferably 10 to 750 g / ha, especially 20 to 500 g / ha.

  In the context of the present invention, the term plant refers to an entire plant, a part of a plant, or a plant propagation material.

  Plants that can be treated with the composition of the present invention as well as the propagation material of said plants include all genetically modified plants or transgenic plants, for example herbicides or fungicides thanks to breeding including genetic engineering methods Crops that are resistant to the action of insecticides or insecticides, or plants with modified characteristics compared to existing plants, which can be generated, for example, by the development of conventional breeding methods and / or mutants, or by recombinant procedures Is included.

  For example, the compositions of the present invention include, but are not limited to, commercial or developing agricultural biotechnology products (see http://www.bio.org/speeches/pubs/er/agri_products.asp Can also be applied to plants that have been modified by breeding, mutagenesis, or genetic manipulation (including as a seed treatment, an inter-spray spray treatment, or by any other means). A genetically modified plant is a plant whose genetic material is so modified by the use of recombinant DNA technology, which is not readily obtainable in the natural environment by cross breeding, mutation or natural recombination It is. In general, one or more genes are integrated into genetically modified plant genetic material to alter certain characteristics of the plant. Such genetic modifications include, but are not limited to, protein (s), oligopeptides or polypeptides, for example by glycosylation or by polymer addition, such as prenylation, acetylation or farnesylation moieties or PEG moieties. Also included is a post-transtional modification of the peptide.

  Plants that have been modified by breeding, mutagenesis, or genetic engineering are treated with, for example, hydroxyphenylpyruvate dioxygenase (HPPD) inhibitors; sulfonylureas (e.g., US 6,222,100, WO01) / 82685, WO00 / 26390, WO97 / 41218, WO98 / 02526, WO98 / 02527, WO04 / 106529, WO05 / 20673, WO03 / 14357, WO03 / 13225, WO03 / 14356, WO04 / 16073) or imidazolinones (e.g., (See US6,222,100, WO01 / 82685, WO00 / 026390, WO97 / 41218, WO98 / 002526, WO98 / 02527, WO04 / 106529, WO05 / 20673, WO03 / 014357, WO03 / 13225, WO03 / 14356, WO04 / 16073) Acetolactate synthase (ALS) inhibitors; Enol pyruvyl shikimate-3-phosphate synthase (EPSPS) inhibitors such as glyphosate (see, for example, WO92 / 00377); Glutamine synthase (GS) inhibition such as glufosinate Agents (see e.g. EP-A 242 236, EP-A 242 246) or oxynyl herbicides (e.g. US 5,559,02 (See 4)) to be resistant to the application of certain classes of herbicides. Some cultivated plants, such as Clearfield® summer rape (Canola, BASF SE, Germany) that is resistant to imidazolinones, such as imazamox, are now resistant to herbicides by conventional breeding methods (mutagenesis). Has been. Genetic engineering methods have been used to ensure that cultivated plants such as soybean, cotton, corn, beets and rapeseed are resistant to herbicides such as glyphosate and glufosinate, some of which are Commercially available under the trademarks RoundupReady® (glyphosate resistant, Monsanto, USA) and LibertyLink® (glufosinate resistant, Bayer CropScience, Germany).

  Furthermore, by using recombinant DNA technology, one or more insecticidal proteins, in particular δ-endotoxins, such as CryIA (b), CryIA (c), CryIF, CryIF (a2), CryIIA (b), CryIIIA Known from bacterial genus Bacillus, in particular Bacillus thuringiensis, such as CryIIIB (b1) or Cry9c; plant insecticidal proteins (VIP), for example VIP1, VIP2, VIP3 or VIP3A; of nematodes that form bacterial colonies Insecticidal proteins, for example, species of the genus Photorhabdus or species of the genus Xenorhabdus; produced by animals such as scorpion toxins, spider toxins, wasp toxins or other insect-specific neurotoxins Toxins; toxins produced by fungi such as Streptomycetes toxins, plant lectins such as peas or barley lectins; agglutinins; trypsin inhibitors, serine protease inhibitors, patachi Proteinase inhibitors such as cystatin or papain inhibitors; ribosome inactivating proteins (RIP) such as lysine, corn-RIP, abrin, ruffin, saporin or bryodin; 3-hydroxysteroid oxidase, ecdysteroid-IDP- Steroid metabolic enzymes such as glycosyl-transferase, cholesterol oxidase, ecdysone inhibitor or HMG-CoA-reductase; ion channel blockers such as sodium or calcium channel blockers; juvenile hormone esterase; diuretic hormone receptor (helicokinin receptor) Plants that can synthesize stilbene synthase, bibenzyl synthase, chitinase or glucanase are also included. In the context of the present invention, these insecticidal proteins or toxins should also be clearly understood as pretoxins, hybrid proteins, cleaved or otherwise modified proteins. Hybrid proteins are characterized by a new combination of protein domains (see for example WO02 / 015701). Further examples of such toxins or genetically modified plants capable of synthesizing such toxins are for example EP-A 374 753, WO93 / 007278, WO95 / 34656, EP-A 427 529, EP-A 451 878, WO03 / 18810 and WO03 / 52073. Methods for producing such genetically modified plants are generally known to those skilled in the art and are described, for example, in the aforementioned publications. These insecticidal proteins contained in genetically modified plants can cause harmful pests, especially beetles (Coleoptera) from all taxonomic groups of arthropods, to plants that produce these proteins. (Coeloptera)), confer resistance to Diptera insects (Diptera) and moths (Lepidoptera), and nematodes (Linear phylum). Genetically modified plants capable of synthesizing one or more insecticidal proteins are described, for example, in the aforementioned publications, some of which produce YieldGard® (Cry1Ab toxin Corn cultivars), YieldGard® Plus (corn cultivars that produce Cry1Ab and Cry3Bb1 toxins), Starlink® (corn cultivars that produce Cry9c toxins), Herculex® RW (Cry34Ab1, Cry35Ab1 And corn cultivars that produce the enzyme phosphinotricin-N-acetyltransferase [PAT]; NuCOTN® 33B (cotton cultivar that produces Cry1Ac toxin), Bollgard® I (produces Cry1Ac toxin) Cotton cultivars), Bollgard® II (cotton cultivars that produce Cry1Ac and Cry2Ab2 toxins); VIPCOT® (cotton cultivars that produce VIP-toxins); NewLeaf® (Cry3A toxin Potato cultivar to produce); B t-Xtra (registered trademark), NatureGard (registered trademark), KnockOut (registered trademark), BiteGard (registered trademark), Protecta (registered trademark), Syngenta Seeds SAS, French-made Bt11 (for example, Agrisure (registered trademark) CB) And Bt176 (a corn cultivar producing Cry1Ab toxin and PAT enzyme), Syngenta Seeds SAS, a French MIR604 (a corn cultivar producing a modified version of Cry3A toxin, see WO03 / 018810), Monsanto Europe SA, made in Belgium MON 863 (a corn cultivar producing Cry3Bb1 toxin), Monsanto Europe SA, Belgian IPC 531 (a cotton cultivar producing a modified version of Cry1Ac toxin), and Pioneer Overseas Corporation, Belgium 1507 (Cry1F toxin and PAT Corn cultivars that produce enzymes).

  Also included are plants that can synthesize one or more proteins that increase their resistance or resistance to bacterial, viral or fungal pathogens through the use of recombinant DNA technology. Examples of such proteins are so-called “lesion-related proteins” (PR proteins, see eg EP-A 392 225), plant disease resistance genes (eg from the Mexican wild potato Solanum bulbocastanum) These proteins with high resistance to bacteria such as potato cultivars expressing resistance genes acting on Phytophthora infestans or T4-lysozyme (e.g. Erwinia amylvora) Potato cultivar). Methods for producing such genetically modified plants are generally known to those skilled in the art and are described, for example, in the aforementioned publications.

  In addition, by using recombinant DNA technology, productivity (e.g. biomass production, grain yield, starch content, oil content or protein content) is increased and resistance to drought, salinity or other growth limiting environmental factors, Also included are plants that can synthesize one or more proteins that increase their resistance to pests and fungi, bacterial or viral pathogens.

  In addition, plants that contain modified amounts of new or new substance content, such as long-chain omega-3 fatty acids that promote health, especially by improving the nutrition of humans or animals by using recombinant DNA technology Also included are crop oils (eg, Nexera® rapeseed, DOW Agro Sciences, Canada) that produce unsaturated omega-9 fatty acids.

  In addition, by using recombinant DNA technology, plants that contain altered amounts of new or new material content, such as potatoes that produce large amounts of amylopectin (e.g. Amflora® Trademark) Potato, BASF SE, Germany).

  The compositions of the invention are useful by both contact (via soil, glass, walls, mosquito nets, carpets, plant parts or animal parts) and ingestion (food or plant parts), as well as nutrient exchange and transfer.

  Preferred application methods are by application to water bodies, soil, cracks and fissures, pastures, compost piles, application via sewage, application to water, application to floors, walls or spraying to the surroundings and bait Is an application.

  According to another preferred embodiment of the present invention, the present invention is for use against non phytophathogenic pests such as ants, termites, wasps, flies, mosquitoes, crickets, grasshoppers or cockroaches. The composition is prepared into a bait preparation.

  The bait can be a liquid, solid or semi-solid preparation (eg a gel). The bait used in the composition is a product that is sufficiently attractive to stimulate insects such as ants, termites, wasps, flies, mosquitoes, crickets or cockroaches to eat the bait. This attractant may be selected from feeding stimulants or pheromone analogs and / or sex pheromones readily known in the art.

  Infectious diseases transmitted by non-phytopathogenic insects (e.g., malaria, dengue and yellow fever, lymphatic filariasis, and leishmaniasis) are controlled using the compositions of the present invention and their respective compositions The method also includes treating the surfaces of huts and homes, spraying with air, and impregnating curtains, tents, clothing, mosquito nets, tsetse fly traps, and the like. Insecticidal compositions for application to fibers, woven fabrics, knitted fabrics, nonwoven fabrics, netting materials or foils and water discharge fabrics preferably comprise a composition comprising the composition of the invention, optionally a repellent and at least one bond A composition comprising an agent.

  The composition of the present invention can be used not only for wooden materials such as wood, boards, and sleepers, and buildings such as houses, barns, and factories, but also for building materials, furniture, leather, textiles, vinyl substances, electric wires and cables. And / or can be used to protect against termites and control them to prevent harm to crops or humans (eg, when pests invade houses and public facilities).

When treating soil or applying to pest dwellings or nests, the amount of active ingredient ranges from 0.0001 to 500 g per 100 m ² , preferably from 0.001 to 20 g per 100 m ² .

Customary application rates in the protection of materials are, for example, from 0.01 g to 1000 g of active compound per m ^{2 of} material to be treated, preferably from 0.1 g to 50 g per m ² .

  Insecticidal compositions for use in impregnating materials are generally 0.001 to 95% by weight, preferably 0.1 to 45% by weight, more preferably 1 to 25% by weight of at least one repellent and / or insecticide. Containing.

  For use in bait compositions, the general content of active ingredient is 0.0001% to 15% by weight, preferably 0.001% to 5% by weight of active compound. The composition used may also contain other additives such as active material solvents, flavoring agents, preservatives, dyes or bittering agents. The attractiveness of the composition can also be enhanced by a special color, shape or texture.

  For use in spray compositions, the composition content of the active ingredient is 0.001 to 80% by weight, preferably 0.01 to 50% by weight, most preferably 0.01 to 15% by weight.

  The present invention further relates to a method for protecting plant propagation material, the method comprising contacting the plant propagation material with a pesticidally effective amount of the composition of the present invention.

  As mentioned at the outset, in a preferred embodiment of the present invention, the composition of the present invention is used to protect seeds and seedling roots and shoots, preferably seeds.

  Seed treatment can be performed in a seed box before planting in a field.

  For seed treatment purposes, the weight ratio of the composition of the invention will generally depend on the properties of the compounds of the composition of the invention.

Conventional formulations that are particularly useful for seed treatment include, for example:
A Liquid (SL, LS)
D Emulsion (EW, EO, ES)
E Suspension (SC, OD, FS)
F Granule wettable powder and water-soluble granules (WG, SG)
G wettable powder and water solvent (WP, SP, WS)
H Gel preparation (GF)
I Powder (DP, DS)
It is.

  These compositions can be applied to plant propagation materials, in particular seeds, diluted or undiluted. These compositions can be applied to plant propagation materials, in particular seeds, diluted or undiluted. The composition, after being diluted 2 to 10 times, gives an active substance concentration of 0.01 to 60% by weight, preferably 0.1 to 40% by weight, in a ready-to-use preparation. Application can be carried out before or during sowing.

  Methods for applying the compounds of the present invention and compositions thereof, respectively, to plant propagation materials, particularly seeds, are known in the art and include, but are not limited to, seed dressing, Seed coating, seed dusting, seed soaking, seed film coating, seed multilayer coating, seed encrusting, dripping on seeds and seed pelleting.

  In a preferred embodiment, the compounds or compositions thereof are each applied onto the plant propagation material by methods such that germination is not induced, for example by seed dressing, seed pelleting, seed coating and seed dusting. .

  In the treatment of plant propagation material (preferably seeds), the application rate of the composition of the invention is generally related to the product to be formulated (usually 10 to 750 g / l of active agent (s)). Including).

  The invention also relates to plant propagation products, in particular seeds, comprising a composition according to the invention as defined above, ie coated with the composition according to the invention and / or containing the composition according to the invention. Plant propagation material (preferably seeds) is a composition of the present invention in an amount of 0.1 g to 10 kg per 100 kg of plant propagation material (preferably seeds), preferably 0.1 g to 1 kg per 100 kg of plant propagation material (preferably seeds). Including.

  Applying the compounds of the composition of the invention separately or together can be accomplished by spraying or dusting seeds, seedlings, plants or soils before or after planting, or before or after plant emergence. To be implemented.

  According to one variant of soil application, a further subject matter of the invention is an intercostal treatment, which comprises a solid or liquid formulation comprising a composition according to the invention with an open intercostal already seeded. Or simultaneously applying the seed and the formulation between the open culms.

  In one particularly preferred embodiment, the composition of the present invention is an emulsion concentrate (also referred to as an emulsion or EC). Emulsion concentrates generally contain at least 10 wt%, for example 10-70 wt% of adjuvants, based on the weight of the emulsion concentrate. Preferably, the EC comprises 0.5-30 wt% insecticide A, 10-70 wt% adjuvant, and up to 100% formulation aid (the formulation aid is particularly preferably 20-70 wt% In the amount of at least one organic solvent, the sum of all components being up to 100 wt%).

  In particular, the EC comprises 1-15 wt% insecticide A, 15-60 wt% adjuvant, 25-60 wt% organic solvent, and optionally up to 100% further formulation aids (all components The total of the maximum is 100wt%).

  Similarly, in a preferred embodiment, the EC comprises 0.5-30 wt% insecticide B, 10-70 wt% adjuvant, and up to 100% formulation aid (the formulation aid is particularly preferably Including at least one organic solvent in an amount of 20-70 wt%, the sum of all components being up to 100 wt%). In particular, the EC comprises 1-15 wt% Pesticide B, 15-60 wt% adjuvant, 25-60 wt% organic solvent, and optionally up to 100% further formulation aids (all components The total of the maximum is 100wt%).

  The present invention further relates to a method of preparing a composition of the present invention comprising the step of contacting a pesticide and an adjuvant. Usually, the contact is carried out when preparing the agrochemical formulation by known means. Component contact can be achieved by conventional equipment at any temperature, such as room temperature. A preferred mixing method is the method applied to prepare the agrochemical composition.

The present invention further includes
a) providing a composition containing a pesticide;
b) providing a composition containing the adjuvant;
c) contacting the composition of steps a) and b).

  Preferably, the composition of step a) is an emulsion concentrate (EC), suspension concentrate (SC) or miniemulsion (ME). In particular, the composition of step a) is an aqueous SC containing the pesticide in suspension form.

  In another specific embodiment, the composition of step a) is an aqueous ME comprising a pesticidal agent in emulsified form. Preferably, the tank mix contains 0.01 to 5 wt% adjuvant.

In a preferred embodiment, the method of preparing an aqueous tank mix comprises:
a) providing an EC, SC or ME composition containing a pesticide;
b) providing a composition containing the adjuvant;
c) contacting the composition of steps a) and b), wherein the adjuvant is a silicone-based adjuvant or a crop oil concentrate.

  The present invention further relates to the use of adjuvants to increase the efficiency of pesticides.

  An advantage of the present invention is, for example, that the composition of the present invention increases the insecticidal efficiency and prolongs the insecticidal efficiency.

  In one particularly preferred embodiment, the composition of the invention is an emulsion concentrate (EC), which comprises at least one alkoxylated fatty alcohol as defined above. The amount of alkoxylated fatty alcohol is generally at least 10 wt%, based on the weight of the emulsion concentrate. Preferably, the EC comprises 0.5-30 wt% insecticide A, 10-70 wt% alkoxylated fatty alcohol, especially an alcohol of formula (A), and up to 100% formulation aid (the formulation aid). The agent in particular comprises at least one organic solvent, preferably in an amount of 20 to 70 wt%, the sum of all components being up to 100 wt%).

In particular, EC represents 1 to 15 wt% of insecticide A, 15 to 60 wt% of an alkoxylated alcohol of formula (A), wherein ^Ra represents in particular linear C ₁₂ -C ₂₂ -alkyl or mixtures thereof , R ^b in particular represents H or C ₁ -C ₄ -alkyl (more preferably H), m, n, p are preferably independently of one another an integer 2 to 5 (more preferably 2 to 3 X, y, z preferably represent, independently of one another, the number 0-50, and x + y + z preferably corresponds to the value 5-50, more preferably 8-25) , 25-60 wt% organic solvent, and up to 100% further formulation aids (total of all components totals up to 100 wt%).

Similarly, preferably, the EC comprises 0.5-30 wt% insecticide A, 10-70 wt% alkoxylated fatty alcohol, in particular an alcohol of formula (A), and up to 100% formulation aids (the said The formulation auxiliaries especially comprise at least one organic solvent, preferably in an amount of 20-70 wt%, the sum of all components being up to 100 wt%). In particular, EC represents 1 to 15 wt% of insecticide B, 15 to 60 wt% of an alkoxylated alcohol of formula (A), where ^Ra represents in particular linear C ₁₂ -C ₂₂ -alkyl or mixtures thereof , R ^b in particular represents H or C ₁ -C ₄ -alkyl (more preferably H), m, n, p are preferably independently of one another an integer 2 to 5 (more preferably 2 to 3 X, y, z preferably represent, independently of one another, the number 0-50, and x + y + z preferably corresponds to the value 5-50, more preferably 8-25) , 25-60 wt% organic solvent, and up to 100% further formulation aids (total of all components totals up to 100 wt%).

  One particular embodiment of the present invention further relates to a method of preparing a composition of the present invention comprising an alkoxylated fatty alcohol. The method includes contacting a pesticide and an alkoxylated fatty alcohol. Usually, the contact is carried out when preparing the agrochemical formulation by known means. Component contact can be achieved by conventional equipment at any temperature, such as room temperature. A preferred mixing method is the method applied to prepare the agrochemical composition.

The present invention further includes
a) providing a composition containing a pesticide;
b) providing a composition containing an alkoxylated fatty alcohol;
c) A method for preparing an aqueous tank mix comprising the step of contacting water with the composition of steps a) and b).

  The invention also relates to an aqueous pesticide formulation comprising a pesticide compound of formula I as defined above in the form of microparticles suspended in an aqueous liquid.

In the aqueous pesticide formulation of the present invention, the pesticide compound of formula I is present in the form of microparticles suspended in an aqueous liquid. The average particle size of the fine particles generally does not exceed 10 μm, preferably in the range of 1 to 5 μm, in particular in the range of 1 to 3 μm. The average particle size referred to herein is the volume average particle size d (0.5) or d (v, 0.5), i.e. 50% by volume of the particles have a diameter exceeding the quoted value, 50% by volume has a diameter less than the quoted value. Therefore, the average particle diameter is also called “volume median diameter”. Such average particle size can be determined by dynamic light scattering (usually performed with a diluted suspension containing 0.01 to 1% by weight of active ingredient A). Those skilled in the art, for example, H. Wiese (D. Distler, Ed.), Aqueous Polymer Dispersions (Wassrige Polymerdispersionen), Wiley-VCH 1999, Chapter 4.2.1, page 40ff and references cited therein; H Auweter, D. Horn, J. Colloid Interf. Sci. 105 (1985), 399; D. Lilge, D. Horn, Colloid Polym. Sci. 269 (1991), 704; and H. Wiese, The method described in D. Horn, J. Chem. Phys. 94 (1991), page 6429 is known. Preferably, the suspending particles, 20 [mu] m, in particular has a d ₉₀ value not exceeding 10 [mu] m, i.e., less than 10 vol% of the particles have a diameter greater than quoted d ₉₀ value, of at least 90 particles The volume% has a diameter less than the quoted _d90 value. Preferably, the suspending particles, 0.2 [mu] m, in particular has a more d ₁₀ value 0.3 [mu] m, i.e., less than 10 vol% of the particles have a diameter of less than quoted d ₁₀ value, at least of the particles 10% by volume, have a diameter greater than quoted d ₁₀ value.

  The amount of the pesticidal compound of formula I in the aqueous formulation is 5-30 wt%, in particular 6-20 wt%, in particular 8-15 wt%, relative to the total weight of the formulation.

The aqueous liquid may be water, or water, a water-miscible organic solvents, such as methanol, ethanol, n- propanol, isopropanol, n- butanol, 2-butanol, such as tert- butanol C ₁ -C ₄ It may be an alkanol or a mixture with C ₂ -C ₄ -polyols such as ethylene glycol, propylene glycol or glycerol. In the liquid, the amount of solvent generally does not exceed 20 wt% relative to the amount of aqueous liquid, or does not exceed 10 wt% relative to the weight of the formulation. Preferably, the total amount of organic solvent in the aqueous formulation does not exceed 10 wt%, in particular 5 wt%, in particular 1 wt%, relative to the total weight of the formulation. The amount of water is 40-88.9%, in particular 55-85.5 wt%, in particular 65-82 wt%, relative to the total weight of the formulation.

Surprisingly, it has been found that in this particular aqueous pesticide formulation, the compound of formula I is present at least in the form of a crystalline material. At least partially crystalline material, when analyzed XRPD (X-ray powder diffractometry) of the material at 25 ° C., at least three of the following reflections, shown as 2θ values and d-spacings in Table 2 below, especially Characterized by the fact that it shows at least four, or at least five, or at least six, or all.

  This at least partial crystalline form of the compound of formula I is also referred to below as hydrate A or form Y. Without being bound by theory, it is believed that the formation of hydrate A is due to the specific interaction between the compound of formula I present in the aqueous formulation and the surfactant system. Furthermore, a specific surfactant system would prevent the formation and crystallization of the compound of formula I, thus allowing the preparation of a stable aqueous formulation of the compound of formula I.

The aqueous pesticide formulation also comprises at least one anionic polymer surfactant having a plurality of SO ³⁻ groups, 6-20 wt%, in particular 8-17 wt%, especially 9-15 wt%, relative to the total weight of the formulation Containing. Suitable anionic polymeric surfactants having multiple SO ³ -groups include, but are not limited to:

. i arylsulfonic acids such as benzene sulfonic acid, phenol sulfonic acid, alkyl benzene sulfonic acid (e.g., toluenesulfonic acid), naphthalene or C ₁ -C ₁₀ - alkyl naphthalene sulfonate such as an alkyl naphthalene sulfonic acid, formaldehyde, and optionally Depending on the choice, urea and its salts, for example condensates with alkaline earth salts, alkali salts or ammonium salts,
ii. lignosulfonate, and
iii e.g., C ₃ -C ₅ monoethylenically unsaturated carboxylic acid monomers, C ₁ -C ₆ alkyl acrylates such as acrylic acid or methacrylic acid and -. C ₃ ~C ₅ monoethylenically unsaturated carboxylic acid monomers such as methacrylate the C ₁ -C ₆ - alkyl esters, C ₂ -C ₆ hydroxyalkyl acrylates and - C ₂ -C ₆ of C ₃ -C ₅ monoethylenically unsaturated carboxylic acid monomers such as methacrylate - hydroxyalkyl esters, such as styrene vinyl aromatic monomers, as well as ethene, propene, 1-butene, isobutene, hexene, (mixture of isobutene dimer) 2-ethyl-hexene, diisobutene, tripropene, tetrapropene, C ₂ -C _12, such as triisobutene - monoolefins (monolefine), optionally in the form of a copolymer with a monoethylenically unsaturated monomer. Ethylenically unsaturated sulfonic acids such as 2-acrylamido-2-methylpropane sulfonic acid, 2-acryloxyethane sulfonic acid, 2-acryloxy-2-methylpropane sulfonic acid, homopolymers of styrene sulfonic acid or vinyl sulfonic acid and Copolymer.

Preferably, the anionic polymeric surfactant having a plurality of SO ³ groups is a salt of a naphthalene sulfonic acid formaldehyde condensate, a salt of an alkyl naphthalene sulfonic acid formaldehyde condensate, and a naphthalene sulfonic acid formaldehyde urea cocondensate (co- selected from condensate) salts. In one particular preferred embodiment, the anionic polymer surfactant having a plurality of SO ³⁻ groups is an alkali metal salt or alkaline earth metal salt of a reaction product (condensate) of naphthalene sulfonic acid and formaldehyde, Particularly suitable examples are Morwet® grades such as Morwet® D400, D425, D440, D450 or D500 (Akzo Nobel), Tamol® NN grade from BASF SE, Surfaron® A 1530 N100 or Surfaron® A 1543 N100 (Synthron) and Tersperse® grades such as Tersperse® 2001, 2020, 2100 or 2425 from Huntsman.

Aqueous pesticide formulations also contain from 0.1 to 10 wt%, in particular from 0.5 to 8 wt%, in particular from 1 to 5 wt% of nonionic surfactants relative to the total weight of the formulation. Suitable nonionic surfactants include the nonionic surfactants described above. Particularly preferred are hereinafter also referred to as poly (C ₂ ~C ₄₎ an alkylene oxide polymer, a polymeric non-ionic surfactant having at least one poly (C ₂ ~C ₄₎ alkylene oxide moieties. Examples of poly (C ₂ -C ₄₎ alkylene oxide polymers are ethylene oxide repeat units and C ₃ -C ₁₀ - non-ionic copolymers comprising alkylene oxide repeat units, in particular at least one poly (ethylene oxide) moiety PEO and C ₃ ~ Block copolymers having at least one polyether moiety PAO derived from C ₄ -alkylene oxide, in particular polyoxyethylene-polyoxypropylene-block copolymers. A further example of a nonionic graft copolymer is a poly (C ₂ -C ₄ ) alkylene oxide polymer containing a polyethylene oxide moiety PEO grafted onto a nonionic hydrophilic polymer backbone.

Of the poly (C ₂ -C ₄ ) alkylene oxide polymers, particularly preferred are poly (ethylene oxide-co-propylene oxide) polymers, particularly poly (ethylene oxide-copolymers) in which ethylene oxide and propylene oxide repeating units are arranged in blocks. -Propylene oxide) polymer.

Poly (C ₂ -C ₄₎ Among the alkylene oxide polymers, particularly preferred are at least 14, especially at least 15, for example 15 to 19, in particular HLB value of 15 to 19 - has a (HLB = Hydrophilic-lipophilic balance) Poly (ethylene oxide-co-propylene oxide) polymers, particularly poly (ethylene oxide-co-propylene oxide) polymers in which ethylene oxide and propylene oxide repeating units are arranged in blocks. The HLB values referred to herein are those by Griffin (WC Griffin, J. Soc. Cosmet. Chem. 1, 311 (1950); 5, 249 (1954). Mollet et al., “Formulation Technology”, first edition, Wiley-VCH Verlags GmbH, Weinheim 2001, pages 70-73 and references cited therein).

Particularly preferred are aqueous formulations in which the nonionic surfactant is selected from the group of nonionic block copolymers. These nonionic block copolymers comprise at least one poly (ethylene oxide) moiety PEO and at least one hydrophobic polyether moiety PAO. PAO moiety, typically, propylene oxide, 1,2-butylene oxide, cis - derived or trans-2,3-butylene oxide, or a C ₃ -C ₄ alkylene oxide such as isobutylene oxide, at least 3, preferably Contains at least 5, in particular 10 to 100 repeating units (number average). Preferably, the PAO moiety comprises at least 50% by weight, more preferably at least 80% by weight of repeating units derived from propylene oxide. The PEO moiety usually comprises at least 3, preferably at least 5, more preferably at least 10 repeating units derived from ethylene oxide (number average). The weight ratio of PEO part to PAO part (PEO: PAO) is usually 1:10 to 10: 1, preferably 1: 2 to 5: 1, more preferably 1: 1 to 4: 1, especially 1.1: 1. It is in the range of ~ 3: 1. Those having a number average molecular weight _MN in the range of more than 1000 and up to 10000, preferably 1100 to 30000, more preferably 1200 to 20000. Generally, the PEO and PAO moieties comprise at least 80%, preferably at least 90%, for example 90-99.5% by weight of the nonionic block copolymer surfactant.

Suitable block copolymers are described, for example, in WO2006 / 002984, in particular those having the formulas P1 to P5 described therein. Nonionic block copolymer surfactants herein include, for example, Pluronic® P 65, P84, P 103, P 105, P 123 and Pluronic® L 31, L 43, L 62, L 62 Trademarks such as LF, L 64, L 81, L 92 and L 121 Pluronic®, Pluraflo® L 860, Pluraflo® such as L 1030 and L 1060; Pluriol® WSB- Pluriol (registered trademark) such as 125, Tetronic (registered trademark) 704, 709, 1104, 1304, 702, 1102, 1302, 701, 901, 1101, 1301 (BASF SE), etc.Tetronic (registered trademark), Agrilan (registered) Trademarks) AEC 167 and Agrilan® AEC 178 (Akcros Chemicals), Antarox® B / 848 (Rhodia), Berol® 370 and Berol® 374 (Akzo Nobel Surface Chemistry), Dowfax (Registered trademark) 50 C15, 63 N10, 63 N30, 64 N40 and 81 N10 (Dow Europe), Genapol (registered trademark) PF (Clariant), Monolan (registered trademark) PB, Monolan (registered trademark) PC, Monolan (registered trademark) Trademark) Monolan (registered trademark) such as PK (Akcros Chemicals), Pano x (registered trademark) PE (Pan Asian Chemical Corporation), Symperonic (registered trademark) PE / L, Symperonic (registered trademark) PE / F, Symperonic (registered trademark) PE / P, Symperonic (registered trademark) PE / T (ICI Symperonic®, such as Surfactants), Tergitol® XD, Tergitol® XH and Tergitol® XJ (Union Carbide), Triton® CF-32 (Union Carbide), Teric PE Series (Huntsman), and Witconol (registered trademark) such as Witconol (registered trademark) APEB, Witconol (registered trademark) NS 500 K are commercially available. Are also particularly preferred, C ₁ -C ₁₀ alkanols poly having a number average molecular weight M _N of 1000 to 5000 daltons is (ethoxylate - propoxylate - co). Particularly preferred examples include Atlox® G 5000 (Akzo Nobel), Tergitol® XD, Pluronic® P105, Pluriol® WSB-125 and the like.

Preferred nonionic graft copolymers, (i) methyl acrylate, methyl methacrylate, such as hydroxyethyl acrylate and hydroxyethyl methacrylate, C ₃ -C ₅ ester of monoethylenically unsaturated carboxylic acid monomer or hydroxyl -C ₂ -C It contains ₃ -alkyl esters and (ii) polyethylene oxide groups, in polymerized form, bonded to the polymer backbone by either ester bonds or ether bonds. In a preferred embodiment, the backbone of these graft copolymers contains methyl methacrylate and polyethylene oxide esters of methacrylic acid in polymerized form, particularly suitable examples are Atlox® 4913 (Akzo Nobel) and the like. It is.

  The aqueous formulations of the present invention may also contain customary additives, such as additives that modify viscosity (thickeners), antifoams, bactericides and antifreeze agents. The amount of additive generally does not exceed 5% by weight, in particular 2% by weight of the total weight of the composition.

  Suitable thickeners are compounds that impart pseudoplastic flow behavior to the formulation, i.e. imparting a high viscosity in the stationary state and imparting a low viscosity in the stirring stage. In this context, polysaccharide-based commercial thickeners such as Xanthan Gum® (Kelzan® from Kelco, Rhodopol® 23 from Rhone Poulenc or Veegum from RT Vanderbilt ( And phyllosilicate based commercial thickeners that can be hydrophobized, such as Attaclay® (from Engelhardt). Xanthan Gum® is a preferred thickener.

  Suitable antifoaming agents for the dispersants of the present invention include, for example, silicone emulsions (e.g., Rhokonsil® from Silikon® SRE, Wacker or Rhodia, etc.), long chain alcohols, fatty acids, organofluorine compounds and That mixture.

  Bactericides can be added to stabilize the composition of the invention against attack by microorganisms. Suitable fungicides are commercially available, e.g. under the trademark Proxel (R) from Avecia (or Arch), or Acticide (R) RS from Thor Chemie, and Kathon (R) MK from Rohm & Haas. Based on isothiazolones, such as

The aqueous pesticide preparation of the present invention includes the following:
(i) providing a suspension of the compound of formula I as a mixture of an aqueous liquid and a surfactant;
(ii) reducing the particle size of the compound of formula I present in the suspension of step (i) to the desired particle size;
(iii) optionally, can be prepared by a method comprising the steps of adding further formulation auxiliaries and an aqueous liquid.

  To prepare the suspension of step (i), any conventional pesticidal compound of formula I, at least a portion of the aqueous liquid, and the surfactants b) and c) can be sheared sufficiently. To form the desired suspension. Suitable mixing devices include in particular high shear mixers such as Ultra-Turrax equipment, static mixers such as systems with mixing nozzles, stirred bead mills, colloid mills, con mills and other homogenizers.

  In general, the order in which the individual components are combined is not critical. However, step (i) first mixes at least a portion of the aqueous liquid and the surfactant until a homogenous mixture is obtained, and then adds the compound of formula I to the homogenous mixture while shearing. It can be advantageous to do so. Thus, step (i) yields a mixture of components a), b), c) and d), in which the compound of formula I is dispersed in the homogeneous phase formed by the aqueous liquid and the surfactant. Present in the form of solid particles. In general, the mixture of components a), b), c) and d) is of formula I with a content in the range of 5-40 wt%, in particular 6-30 wt%, in particular 8-25 wt%, based on the total weight of the slurry. Obtained from step (i) in the form of a slurry with the compound.

  In general, the solid compound of formula I used in the preparation of the suspension of step (i) may be amorphous, crystalline or semi-crystalline and in particulate form, for example, powder, crystal, granular Or powdered solidified melt. The particles of solid active compound can be regular or irregularly shaped, for example spherical or substantially spherical, or acicular. In general, the solid pesticide compound particles are greater than 1 μm, such as 1.5-1000 μm, especially 2-100 μm, more specifically 2.5 μm, as determined by dynamic light scattering, before being introduced into step (i). It has an average dimension in the range of ~ 50 μm.

  For the mixture obtained from step (i), ie in the form of a suspension, means suitable for reducing the particle size of the a.i. particles present in the mixture to the desired particle size are applied. Step (ii) is performed by any physical friction method such as crushing, crushing or fine crushing, in particular, for example, bead mill crushing, hammer mill crushing, jet mill crushing, air classification mill crushing, pin mill crushing, low temperature crushing etc. It can be carried out by wet grinding or wet grinding. Steps (i) and (ii) are usually performed thereafter. However, it is also possible to carry out these steps together.

  In a preferred embodiment of the invention, step (ii) is performed by bead milling. In particular, it has been found that bead sizes in the range 0.05 to 5 mm, more specifically 0.2 to 2.5 mm, most specifically 0.5 to 1.5 mm are suitable. In general, bead loadings in the range of 40-99%, in particular 70-97%, more specifically 65-95% can be used.

  Step (ii) is carried out in an apparatus suitable for this purpose, in particular an apparatus suitable for wet grinding or wet grinding processes, required by the presence of solvent b. Such devices are generally known. Therefore, step (ii) is preferably a ball mill or bead mill, a stirring ball mill, a circulation mill (stirring ball mill equipped with a pin grinding system), a disk mill, an annular chamber mill, a double cone mill, a three roll mill, a batch mill, a colloid mill. And a mill such as a sand mill. In order to dissipate the thermal energy introduced during the grinding process, the grinding chamber is preferably fitted with a cooling system. Particularly suitable are DRAISWERKE, INC. 40 Whitney Road. Mahwah, ball mill Drais Superflow DCP SF 12, manufactured by NJ 07430 USA, Drais Perl Mill PMC, DRAISWERKE, INC. GmbH, Selb, Germany-made disc mill, Eiger Machinery, Inc., 888 East Belvidere Rd., Grayslake, IL 60030 USA-made bead mill Eiger Mini 50, and WA Bachofen AG, Switzerland-made bead mill DYNO-Mill KDL.

  The time required to reduce the particle size depends on the desired grade of fineness of the active compound particles or the desired particle size in a manner known per se and can be determined by the person skilled in the art in standard experiments. For example, milling times in the range of 1 to 48 hours have been found suitable, but longer times are also conceivable. A grinding time of 2 to 24 hours is preferred.

  The pressure and temperature conditions during pulverization are generally not so important and thus, for example, atmospheric pressure has been found suitable. For example, temperatures in the range of 10 ° C. to 100 ° C. have been found to be suitable, and the temperature chosen is usually the temperature at which the active compound a) is present as a solid.

  To the aqueous formulation obtained from step ii, further formulation additives, such as thickeners, can optionally be added along with additional water / aqueous liquids as required.

  Aqueous formulations exhibit high storage stability with no or significant increase in suspended particle size due to particularly undesirable Ostwald ripening.

  As indicated above, the present invention also relates to hydrate A as defined above. Hydrate A is an at least partially crystalline non-stochiometric hydrate of the compound of formula I. This hydrate is believed to be stable in the aforementioned aqueous pesticide formulation but appears to be unstable in the absence of aqueous liquid and surfactant.

  As pointed out above, a further aspect of the present invention relates to hydrate B of the compound of formula I. Form B is a non-stoichiometric hydrate of the compound of formula I. Typical water content is in the range 7.5-9 wt%, especially about 8.5 wt%, ie 8.5 ± 0.2 wt%. The water content can be determined by thermogravimetric analysis (TGA). Form B exhibits desolvation at temperatures in the range of 65-70 ° C, especially 66-68 ° C, resulting in an amorphous compound of formula I. Form B is stable at room temperature in the presence of mother liquor or water, but slowly converts to Form C below when the mother liquor is removed or enters the amorphous material as Form B dries.

Form B can be at least partially miscible (eg, at least 20 wt% miscibility at 25 ° C.) with, for example, water-containing organic solvents, particularly water, or preferably completely miscible with water (25 C.) and can be prepared by crystallization from an organic solvent containing water. Suitable organic solvents are C ₁ -C ₄ alkanols such as ethanol or isopropanol, cyclic ethers such as acetone, dimethyl sulfoxide, acetonitrile, or tetrahydrofuran. In order to obtain Form B, the water content in the organic solvent containing water is 20 to 90 wt%.

  Crystallization can be achieved by conventional techniques such as evaporation crystallization or precipitation crystallization. In precipitation crystallization or evaporative crystallization, the compound of formula I is dissolved in an aqueous organic solvent containing water or dissolved in a dry organic solvent and then water is added. Crystallization can be performed by cooling or adding additional water to reduce the solubility of the compound of formula I in an organic solvent containing water. Alternatively, crystallization can be performed by removing the solvent, for example by evaporation. Addition of Form B seed crystals serves to quantitatively convert Compound I to Form B. Preferably, precipitation crystallization or evaporative crystallization is carried out at a temperature in the range of 0-60 ° C, especially 5-50 ° C.

Form B can also be prepared by crystallization of a slurry, the crystallization comprising providing a slurry of the compound of formula I in water or an organic solvent containing water. Thereby, the solid compound of formula I is converted to Form B. For the purpose of crystallization of the slurry, an aqueous organic solvent or water can be used. The amount of water in the solvent used for crystallization of the slurry can range from 10 to 100 wt%. Suitable organic solvents are, C ₁ -C ₄ alkanols, ethylene glycol, such as ethanol or isopropanol, glycerol, cyclic ethers acetone, dimethyl sulfoxide, acetonitrile, or the like tetrahydrofuran. Preferably, the crystallization of the slurry is carried out at a temperature in the range of 0-60 ° C, especially 5-50 ° C. The time required for conversion to Form B can range from 1 hour to 10 days, depending on temperature and solvent. Conversion to Form B can be accelerated by subjecting the slurry to mechanical shearing, for example by milling. Addition of Form B seed crystals serves to quantitatively convert Compound I to Form B.

  As the starting material for crystallization, any crystalline or amorphous form of the compound of formula I can be used.

  Form B is stable at room temperature when in contact with an aqueous solvent or water, or at high humidity, e.g. 90%, but slowly when the mother liquor is removed or the humidity is reduced to Form C below Convert. Form B slowly converts to an amorphous material when dried at high temperatures, for example> 50 ° C. Form B can provide excellent formulation stability for aqueous formulations.

  Furthermore, a further aspect of the invention relates to hydrate C of the compound of formula I. Form C is a further non-stoichiometric hydrate of the compound of formula I. Typical water content is in the range of 6.5-8 wt%, especially about 7.6 wt%, ie 7.6 ± 0.2 wt%. The water content can be determined by thermogravimetric analysis (TGA). Form C exhibits desolvation at a temperature in the range of 55-60 ° C, especially 56-58 ° C, resulting in an amorphous compound of formula I.

  Form C is obtained from Form B by removing the mother liquor from the crystalline material of Form B and storing the solid thus obtained at ambient conditions (e.g., 5-30 ° C., 10% to <90% humidity). be able to. Form C can also be obtained as an intermediate in a slurry experiment to produce Form B.

  Form C is stable at ambient conditions for weeks and months and is therefore particularly useful for preparing solid formulations of compounds of formula I.

  The invention is further illustrated by the following figures and examples.

Starting material:
Insecticide A: Insecticide of formula (I).

Insecticide B: Insecticide of formula (II).

Adjuvant A: 83% paraffinic petroleum, 17% sorbitan fatty acid ester and polyethoxylated sorbitan fatty acid ester commercially available as Agridex® from Bayer Crop Science.

Adjuvant B: Polydimethylsiloxane modified with polyalkylene oxide, poly (ethylene oxide-block-propylene oxide, and a small amount of anti-foaming polypropylene oxide butyl oleate, commercially available from Helena as Kinetic® Molecular Zippering Action.

Adjuvant C: ethoxylated and propoxylated linear C ₁₆ / C ₁₈ alcohol, liquid at room temperature, wetting power by immersion:> 240 seconds (according to DIN 1772 at 1 g / L in 2 g / l sodium carbonate at room temperature) Water content 5-10 wt%, surface tension: 30-35 mN / m (according to DIN 14370 at 1 g / L at room temperature), pH in water about 7.

Surfactant 1: Sodium salt of naphthalenesulfonic acid formaldehyde condensate-Morwet® D425 (Akzo Nobel).

Surfactant 2: Poly -C ₂ ~C ₃ - C ₁ ~C alkylene glycol ₉ - alkyl ethers (M _N 2900) -Atlox (TM) G5000 (Croda), HLB 17 .

Surfactant 3: Polyoxyethylene graft copolymer Atlox® 4913, Croda.

Antifoaming agent: Silicon-based defoaming agent.

Preservative: Acticide MBS (Thor).

Thickener: xanthan gum.

analysis:
The X-ray powder diffraction (XRPD) reported herein and shown in FIGS. 1, 2 and 3 is 2θ = 3 ° using a Panoramic X'Pert Pro diffractometer (Manufacturer: Panaltical) in a reflective configuration. Recorded using Cu-K _alpha rays (at 25 ° C.) in increments of 0.0167 ° in the range of ˜35 °. Using the recorded 2θ values, the surface spacing d of the presentation was calculated. Peak intensity (y-axis: linear intensity count) is plotted against 2θ angle (x-axis, depending on 2θ degrees).

  DSC was performed on a Mettler Toledo DSC 822e module. The sample was placed in an aluminum pan that was crimped but had a vent. The sample size in each case was 5-10 mg. Thermal behavior was analyzed in the range of 30-250 ° C. The heating rate was 5 ° C./min. The sample was purged with a flow of nitrogen at 150 ml / during the experiment.

  Melting point values were confirmed by Mettler Hot Stage in combination with an optical microscope.

  The particle size distribution was determined using a Malvern Mastersizer 2000.

Example 1
Stable suspension concentrate The following composition: 9.4 wt% Pesticide A, 3 wt% surfactant 2, 10 wt% surfactant 1, 0.2 wt% xanthan gum, 0.4 wt% antifoam, 0.16 wt Suspension concentrate (SCA) with% preservative and up to 100 wt% water was prepared by wet bead milling. The average particle size was about 1-2 μm.

  The formulation was prepared as follows. Insecticide A, Surfactant 1, Surfactant 2, a portion of water, a portion of defoamer and a preservative were mixed together in a suitable container using a Silverson high shear mixer. The mixture was then ground in a bead mill with a ball load sufficient to ensure effective milling efficiency. The temperature of the grinding head was controlled at 5 ° C. When the desired particle size distribution was obtained, milling was stopped (measured with Malvern Mastersizer 2000). Finally, the thickener and the remaining antifoam were added to the previous sample with stirring to ensure that the components were evenly distributed.

Samples of the aqueous formulation thus obtained were stored for 3 months under various storage conditions and analyzed for the particle size of the suspended particles before and after storage. The results are summarized in Table 3.

Two additional samples were stored for 1 month at -20 ° C and 60 ° C, respectively. The crystalline form before / after storage was characterized by XRPD. The X-ray powder diffraction measured at 25 ° C. and Cu—K _α- ray before storage is shown in FIG. This X-ray powder diffraction is reflected as the following 2θ values: 9.7 ± 0.2 °, 10.3 ± 0.2 °, 11.3 ± 0.2 °, 14.0 ± 0.2 °, 15.5 ± 0.2 °, 16.4 ± 0.2 °, 17.6 ± 0.2 ° Indicates. Similar XRPDs with the same reflex were found after storage, indicating that Form A was present in the formulation both before and after storage.

Comparative Example C1
The following composition: 9.4 wt% insecticide A, 3 wt% surfactant 2, 10 wt% surfactant 3, 0.2 wt% xanthan gum, 0.4 wt% antifoam, 0.15 wt% preservative, 10 wt A suspension concentrate (SC B) with% urea and up to 100 wt% water was prepared by wet bead milling. The average particle size (d ₅₀ ) was about 1-2 μm.

A significant increase in particle size was observed after 2 weeks storage at 54 ° C. d The increase in the ₅₀ value exceeded 50% of the initial value.

Example 2
Improving the efficiency of SC formulations containing tank mix adjuvants The following composition: 9.4 wt% Pesticide A, 3 wt% poly (ethylene glycol-block-propylene glycol), 10 wt% naphthalenesulfonate condensate salt, 0.2% Suspension concentrate (SCA) with xanthan gum, 0.4 wt% antifoam, 0.16 wt% preservative and up to 100 wt% water was prepared by wet bead milling. The average particle size was about 1-2 μm. After mixing SC A, water was applied to obtain a spray mix of Insecticide A having the desired concentration. Adjuvant A or B was then added to the previous composition at the desired concentration. The following conditions were used: spray volume 300 l / ha, pesticide A usage rate 10 g / ha, concentration of adjuvant A or B in spray mix of 1 wt% or 0.25 wt% respectively, 0.25% or 0.1% respectively.

Spray application and biological testing: Spray application was performed with the spray mix in a spray chamber. A "U" boom with three nozzles spraying on the top and bottom of the foliage was used to spray the pepper plant variety California Wonder. Each treatment was repeated four times, with one iteration representing one pepper plant. Treated pepper plants were maintained in a greenhouse allowing UV transmission. The plants were then infested with peach aphids at various intervals after treatment (2, 7 and 15 days; DAT). Treated and then parasitized plants were maintained in a maintenance room at 27 ° C. under constant fluorescence for 6 days and then compared to the control plants by the number of surviving aphids relative to control plants. (%) Was evaluated. The results are summarized in Table 4. In comparison to compositions without adjuvants, significant efficiency improvements were found for compositions containing adjuvants.

Example 3
Efficiency improvement following composition of EC formulations adjuvants are incorporated: 5.0 wt% of the pesticide A, 6 wt% of the calcium salt of dodecylbenzenesulfonic acid, according ethoxylated iso -C ₁₃ alcohols (DIN 53 914 of 11.5 wt% , 1 g / l at 23 ° C. in distilled water, surface tension 27-29 mN / m), 8 wt% poly (ethylene glycol-block-propylene glycol), 30 wt% adjuvant B, 10.5 wt% 2-heptanone and 29 wt An emulsion concentrate (EC A) with% heavy aromatic solvent naphtha (initial boiling point 240 ° C.) was prepared. A comparative EC Comp1 was prepared as EC A by replacing Adjuvant B with the corresponding amount of heavy aromatic solvent naphtha.

After mixing EC A, water was applied to obtain a spray mix of Insecticide A having the desired concentration. The following conditions were used: spray volume 300 l / ha, pesticide A usage rate 10 g / ha. Spray application and biological tests were performed as described in Example 2. The results are summarized in Table 5. In comparison to the formulation without Adjuvant B, Adjunct B was found to significantly improve the efficiency of the formulation.

Example 4
Tank mix adjuvants efficiency improvement following composition of ME formulation comprising: 5.0 wt% of the pesticide A, 6 wt% of the calcium salt of dodecylbenzenesulfonic acid, according ethoxylated iso -C ₁₃ alcohol (DIN 53914 of 13 wt%, 1 g / l at 23 ° C in distilled water, surface tension 27-29 mN / m), 4 wt% triblock polymer EO / PO / EO, 12 wt% 2-heptanone, 18 wt% heavy aromatic solvent naphtha (initial boiling point) 240 ° C), 20 wt% propylene glycol, 0.02 wt% citric acid monohydrate, 0.2 wt% biocide, and miniemulsion / microemulsion (ME A) with up to 100 wt% water.

After mixing ME A, water was applied to obtain a spray mix of Insecticide A having the desired concentration. The following conditions were used: spray volume 300 l / ha, pesticide A usage rate 10 g / ha, adjuvant A1 wt%. Spray application and biological tests were performed as described in Example 2. The results are summarized in Table 6. In comparison to a formulation without adjuvant A, adjuvant A was found to significantly improve the efficiency of the formulation.

Example 5
Improving the efficiency of SC formulations containing tank mix adjuvants After mixing the suspension concentrate SC A of Example 2, water was applied to obtain a spray mix of Insecticide A having the desired concentration. Adjuvant C was then added to the previous mixture at the desired concentration. The following conditions were used: spray volume 300 l / ha, pesticide A usage rate 10 g / ha, concentration of adjuvant C in the spray mix, 1%, 0.25% or 0.1%, respectively.

  Spray application and biological testing: Spray application was performed with the spray mix in a spray chamber. A "U" boom with three nozzles spraying on the top and bottom of the foliage was used to spray the pepper plant variety California Wonder. Each treatment was repeated four times, with one iteration representing one pepper plant. Treated pepper plants were maintained in a greenhouse allowing UV transmission. The plants were then infested with peach aphids at various intervals after treatment (2, 7 and 15 days; DAT). Treated and then parasitized plants were maintained in a maintenance room at 27 ° C. under constant fluorescence for 6 days and then compared to the control plants by the number of surviving aphids relative to control plants. (%) Was evaluated.

The results are summarized in Table 7. In comparison to the formulation without Adjuvant C, Adjunct C was found to significantly improve the efficiency of the formulation at all concentrations.

Example 6
Improving the efficiency of EC formulations incorporating adjuvants The following composition: 5.0 wt% pesticide A, 6 wt% polyarylphenyl ether sulfate ammonium salt, 11.5 wt ethoxylated fatty alcohol with an average of 5 mol EO (HLB value 10-11), 8 wt% poly (ethylene glycol-block-propylene glycol), 20 wt% adjuvant C, 10.5 wt% 2-heptanone and 39 wt% heavy aromatic solvent naphtha (initial boiling point 240 An emulsion concentrate (EC B) was prepared. Comparative formulation “EC Comp2” was prepared as EC B by substituting Adjuvant C with the corresponding amount of heavy aromatic solvent naphtha.

After mixing EC A, water was applied to obtain a spray mix of Insecticide A having the desired concentration. The following conditions were used: spray volume 300 l / ha, 1500 l / ha, pesticide A usage rate 10 g / ha, respectively. Spray application and biological testing were performed as described in Example 5. The results are summarized in Table 8. In comparison to a formulation without Adjuvant C, Adjunct C was found to significantly improve the efficiency of the formulation.

Example 7
Improving the efficiency of SC formulations containing tank mix adjuvants.Adjuvant mixture D was mixed with 50 wt.% Adjuvant C, 10 wt.% Atplus. Low moisture blend of ester and polyoxyethyl sorbitan fatty acid ester), and 40 wt% low molecular weight paraffinic oil (CAS64741-89-5).

  Adjuvant Mixture E was prepared by mixing 50 wt% Adjuvant C, 10 wt% Atplus® 300F-SP and 40 wt% low molecular weight paraffinic oil (boiling point 270-320 ° C).

  After mixing SC A (from Example 2), water was applied to obtain a spray mix of the active ingredient having the desired concentration. Next, adjuvant mixture D or adjuvant mixture E was added to the previous mixture at the desired concentration. In this experiment the following conditions were used: spray volume 300 l / ha, active ingredient usage 10 g / ha, concentration of adjuvant mixture A or B 0.2 wt%.

Spray application and biological testing were performed as described in Example 5. The results are summarized in Table 9. A significant improvement in efficiency was found for the composition containing the adjuvant in comparison to the composition without the adjuvant.

Example 8
Improving the efficiency of SC formulations containing tank mix adjuvants Adjuvant Mixture F was mixed with 50 wt% Adjuvant C and 50 wt% linear fatty alcohol alkoxylate (wet at 1 g / L at room temperature according to EN 1772 for 22-32 sec. ) Was mixed. Adjuvant Mixture G was prepared by mixing 90 wt% Adjuvant C and 10 wt% fatty alcohol alkoxylate (same as Mixture F). Adjuvant Mixture H was prepared by mixing 75 wt% alcohol alkoxylate A and 25 wt% fatty alcohol alkoxylate (same as Mixture F).

  After mixing SC A (from Example 2), water was applied to obtain a spray mix of the active ingredient having the desired concentration. Adjuvant mixture F, G or H was then added to the previous mixture at the desired concentration. In this experiment, the following conditions were used: spray volume 300 l / ha, active ingredient usage 10 g / ha, concentration of adjuvant mixture F, G or H 0.1 wt%.

Spray application and biological testing were performed as described in Example 5. The results are summarized in Table 10. A significant improvement in efficiency was found for compositions containing small amounts of adjuvants in comparison to compositions without adjuvants.

Example 9
Improving the efficiency of EC formulations incorporating adjuvants The following composition: 5.5 wt% insecticide A, 14 wt% polyarylphenyl ether sulfate ammonium salt, 8 wt% poly (ethylene glycol-block-propylene glycol), 40 wt% Branched fatty alcohol alkoxylates (wet power by immersion at 1 g / L in 2 g / l sodium carbonate at room temperature according to DIN 1772; 10 to 100 seconds; surface tension: 20-29 mN / m (1 g / L at room temperature according to DIN 14370) )), An emulsion concentrate (EC C) with 14 wt% 2-heptanone and 19 wt% heavy aromatic solvent naphtha (initial boiling point 240 ° C.) was prepared.

  Comparative EC Comp3 was prepared as ECC by replacing the branched fatty alcohol alkoxylate with the corresponding amount of heavy aromatic solvent naphtha.

After mixing the ECC, water was applied to obtain a spray mix of Insecticide A having the desired concentration. The following conditions were used: spray volume 300 l / ha, pesticide A usage rate 10 g / ha. Spray application and biological tests were performed as described in Example 2. The results are summarized in Table 11.

Example 9
Improving the efficiency of EC formulations without adjuncts: An emulsion concentrate (EC D) was prepared with 2-heptanone and 59 wt% heavy aromatic solvent naphtha (initial boiling point 240 ° C).

After mixing EC D, apply water (comparison) or apply water containing either 0.5% v / v Adjuvant A or Adjuvant C to achieve the desired concentration of Insecticide A A spray mix was obtained. The following conditions were used: spray volume 300 l / ha, pesticide A usage rate 0.3 g / h or 10 g / ha. Spray application and biological tests were performed as described in Example 2. The results are summarized in Table 11.

Example 10
Preparation of Form B by Slurry Experiment The amorphous compound of formula I or the compound of formula I in the form of a mixture of amorphous and partially crystalline material is stirred into water or an aqueous solvent as shown in Table 12 below. Suspended while. After the time shown in Table 12 had elapsed, the slurry was filtered and the resulting material was immediately analyzed by X-ray powder diffractometry at 25 ° C. and Cu- _Kα radiation. In each case, Form B was obtained. In Example 10-L, the suspension was pulverized as described in Example 1.

The hydrate form B thus obtained has the X-ray powder diffraction shown in FIG. XRPD (at 25 ° C and Cu-K _α- ray) has the following 2θ values: 8.0 ± 0.2 °, 9.5 ± 0.2 °, 10.7 ± 0.2 °, 11.0 ± 0.2 °, 11.2 ± 0.2 °, 11.7 ± 0.2 °, 14.2 Reflections given as ± 0.2 °, 15.6 ± 0.2 °, 16.5 ± 0.2 °, 17.7 ± 0.2 °, 21.5 ± 0.2 ° were shown.

Example 11
Preparation of Form B by Precipitation Experiment A compound of formula I in the form of a mixture of amorphous and partially crystalline material was dissolved in an organic solvent as shown in Table 13 below at 22 ° C. with stirring. Next, water was added dropwise with stirring until precipitation occurred. The precipitated material was filtered off and immediately analyzed by X-ray powder diffractometry at 25 ° C. and Cu—K _α- ray. In each case, Form B was obtained.

Example 12
Preparation of Form C by Drying Form B Form B obtained from Example 11 was left on filter paper for 16 hours at ambient conditions. The material thus obtained was analyzed by X-ray powder diffraction method at 25 ° C. and Cu—K _α- ray. The XRPD thus obtained has the following 2θ values: 7.5 ± 0.2 °, 9.6 ± 0.2 °, 11.0 ± 0.2 °, 11.7 ± 0.2 °, 12.1 ± 0.2 °, 12.5 ± 0.2 °, 15.8 ± 0.2 °, 16.3 ± 0.2 Reflections given as °, 17.4 ± 0.2 °, 19.3 ± 0.2 ° and 19.6 ± 0.2 ° were shown.

Example 13
Preparation of Form C by Slurry Experiment and Subsequent Drying Amorphous compound of formula I, or a compound of formula I in the form of a mixture of amorphous and partially crystalline material, water or an aqueous solvent as shown in Table 14 below And suspended with stirring for at least 2 days. The slurry was then filtered and the resulting material was left on filter paper for 16 hours at ambient conditions. The material thus obtained was analyzed by X-ray powder diffraction method at 25 ° C. and Cu—K _α- ray. In each case, Form C was obtained.

Claims (42)

Pyripyropene pesticide of formula I or formula II

And a composition comprising an adjuvant.   2. The composition of claim 1, wherein the pyripyropene pesticide is a pesticide of formula I.   The composition according to claim 1 or 2, wherein the adjuvant comprises a nonionic surfactant. Adjuvant, at least one poly -C ₂ -C ₄ - contains a nonionic surfactant having an alkylene oxide moiety, composition of claim 3. Surfactant having at least one poly-C ₂ -C ₄ -alkylene oxide moiety is modified with polyethoxylated sorbitan fatty acid ester, poly (ethylene oxide-co-propylene oxide) copolymer and poly-C ₂ -C ₄ -alkylene oxide 5. A composition according to claim 4 selected from selected polydimethylsiloxanes.   The composition according to any one of claims 1 to 5, wherein the adjuvant comprises a silicone-based adjuvant. The composition according to any one of claims 1 to 6, wherein the silicone adjuvant comprises polydimethylsiloxane modified with poly-C ₂ -C ₄ -alkylene oxide.   8. A composition according to any one of claims 1 to 7, wherein the adjuvant comprises a crop oil concentrate.   9. A composition according to any one of claims 1 to 8, wherein the crop oil concentrate contains at least one hydrocarbon solvent and at least one nonionic surfactant.   4. The composition according to any one of claims 1 to 3, wherein the adjuvant comprises an alkoxylated fatty alcohol. 11. Composition according to claim 10, wherein the alkoxylate is selected from alkoxylates of the formula (A)
R ^a -O- (C _m H _2m O) _x- (C _n H _2n O) _y- (C _p H _2p O) _z -R ^b (A)
[Where
R ^a represents C ₅ -C ₃₆ -alkyl, C ₅ -C ₃₆ -alkenyl or a mixture thereof,
R ^b represents H or C ₁ -C ₁₂ -alkyl,
m, n and p each independently represent an integer 2 to 16,
x, y, and z each independently represent a number 0 to 100,
x + y + z corresponds to a value of 1-100]. 12. A composition according to claim 10 or 11, wherein R ^a represents linear C ₅ -C ₃₆ -alkyl, C ₅ -C ₃₆ -alkenyl or a mixture thereof. R ^a is a straight-chain C ₁₄ -C ₃₆ - alkyl, C ₁₄ -C ₃₆ - alkenyl, or mixtures thereof A composition according to any one of claims 10 to 12.   The composition according to any one of claims 10 to 13, wherein m, n and p each independently represent an integer of 2 to 5.   14. A composition according to any one of claims 10 to 13, wherein x + y + z corresponds to a value of 10-30.   16. A composition according to any one of claims 1 to 15, in the form of an emulsion comprising at least 10 wt% of adjuvants relative to the composition.   8. A composition according to any one of claims 6 or 7, in the form of an emulsion comprising at least 10 wt% silicone adjuvants relative to the composition.   10. A composition according to any one of claims 8 or 9, in the form of an emulsion comprising at least 10 wt% crop oil concentrate relative to the composition.   16. A composition according to any one of claims 10 to 15, in the form of an emulsion comprising at least 10 wt% alkoxylated fatty alcohol relative to the composition.   The composition according to any one of claims 1 to 15, in the form of a tank mix, containing from 0.01 to 5 wt% of adjuvants relative to the total weight of the tank mix.   8. A composition according to any one of claims 6 or 7, in the form of a tank mix, containing from 0.01 to 5 wt% of a silicone adjuvant relative to the total weight of the tank mix.   10. A composition according to any one of claims 8 or 9, in the form of a tank mix, containing from 0.01 to 5 wt% of a crop oil concentrate relative to the total weight of the tank mix.   16. A composition according to any one of claims 10 to 15, in the form of a tank mix, containing 0.01 to 5 wt% alkoxylated fatty alcohol relative to the total weight of the tank mix.   24. A composition according to any one of claims 1 to 23, wherein the pesticide is present in dissolved or suspended form.   25. A method of preparing a composition according to any one of claims 1 to 24 comprising the step of contacting the pesticide and the adjuvant. a) providing a composition containing a pesticide as defined in claim 1 or 2;
b) providing a composition containing an adjuvant as defined in claim 1 or any one of claims 3 to 15;
c) contacting the composition of steps a) and b) with an aqueous tank mix.   27. A method according to claim 26, wherein the tank mix contains 0.01 to 5 wt% of adjuvants relative to the total weight of the tank mix.   Use of an adjuvant as defined in claim 1 or any one of claims 3 to 15 for increasing the efficiency of a pesticide as defined in claim 1.   A kit comprising a) a pesticide as defined in claim 1 or 2 and b) an adjuvant as defined in any one of claims 1 or 3 to 15 as separate components for use in combination. Ob parts. a) 5-30 wt% of the pesticide compound of formula I relative to the total weight of the formulation;
b) 6-20 wt% of the total weight of the formulation, at least one anionic polymer surfactant having a plurality of SO ³ -groups;
c) 0.1 to 10 wt% of at least one nonionic surfactant relative to the total weight of the formulation;
d) an aqueous pesticide comprising a pesticide compound of formula I as defined in claim 1 in the form of microparticles suspended in an aqueous liquid comprising 40 to 88.9% by weight of water relative to the total weight of the formulation Formulation.   31. The aqueous pesticide formulation according to claim 30, wherein the volume average diameter of the pesticide particles is 1-5 μm. Pesticides are 25 ° C and Cu-K _α- ray by X-ray powder diffraction, the following 2θ values: 9.7 ± 0.2 °, 10.3 ± 0.2 °, 11.3 ± 0.2 °, 14.0 ± 0.2 °, 15.5 ± 0.2 ° 32. Aqueous pesticide formulation according to claim 30 or 31, wherein said product is present in the form of a material exhibiting at least three of the reflections given as 16.4 ± 0.2 °, 17.6 ± 0.2 °. The anionic polymeric surfactant having multiple SO ^3- groups is selected from a salt of a naphthalene sulfonic acid formaldehyde condensate, a salt of an alkyl naphthalene sulfonic acid formaldehyde condensate, and a salt of a naphthalene sulfonic acid formaldehyde urea cocondensate 33. An aqueous pesticide formulation according to any one of claims 30 to 32. Nonionic surfactants, poly (C ₂ ~C ₄₎ is selected from alkyl alkylene oxide polymers, aqueous pesticidal formulation according to any one of claims 30 33.   35. Aqueous pesticide formulation according to any one of claims 30 to 34, wherein the nonionic surfactant is selected from poly (ethylene oxide-co-propylene oxide) polymers having at least 12 HLB. By X-ray powder diffraction at 25 ° C and Cu-K _α- ray, the following 2θ values: 9.7 ± 0.2 °, 10.3 ± 0.2 °, 11.3 ± 0.2 °, 14.0 ± 0.2 °, 15.5 ± 0.2 °, 16.4 ± 0.2 °, A crystalline hydrate of a compound of formula I as defined in claim 1 which exhibits at least four of the reflections given as 17.6 ± 0.2 °. By X-ray powder diffraction at 25 ° C. and Cu-K _α ray, the following 2θ values: 8.0 ± 0.2 °, 9.5 ± 0.2 °, 10.7 ± 0.2 °, 11.0 ± 0.2 °, 11.2 ± 0.2 °, 11.7 ± 0.2 °, 14.Crystalline hydration of a compound of formula I as defined in claim 1 showing at least four of the reflections given as 14.2 ± 0.2 °, 15.6 ± 0.2 °, 16.5 ± 0.2 °, 17.7 ± 0.2 °, 21.5 ± 0.2 ° object. By X-ray powder diffraction at 25 ° C and Cu-K _α- ray, the following 2θ values: 7.5 ± 0.2 °, 9.6 ± 0.2 °, 11.0 ± 0.2 °, 11.7 ± 0.2 °, 12.1 ± 0.2 °, 12.5 ± 0.2 °, Crystalline hydration of a compound of formula I as defined in claim 1 showing at least four of the reflections given as 15.8 ± 0.2 °, 16.3 ± 0.2 °, 17.4 ± 0.2 °, 19.3 ± 0.2 ° and 19.6 ± 0.2 ° object.   20. A method for protecting a plant from attack or parasitism by insects, ticks or nematodes, wherein the plant or soil or water on which the plant grows and a pesticidally effective amount. 36. A method comprising contacting the composition according to claim 1 or a pesticide effective amount of the aqueous pesticide formulation according to any one of claims 30 to 35.   A method for controlling insects, spiders or nematodes, wherein the insects, ticks or nematodes, or their food supply, habitat, hotbed or their location and a pesticidally effective amount 36. A method comprising contacting the composition of claim 1 or a pesticide effective amount of the aqueous pesticide formulation of any one of claims 30 to 35.   A method for protecting plant propagation material comprising a plant propagation material and a pesticidally effective composition as defined in any one of claims 1 to 19, or a pesticidal effective amount of claims 30 to 35. A method comprising the step of contacting with the aqueous pesticide formulation according to any one of the above.   27. A seed comprising the composition of any one of claims 1 to 26.

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